WO2015080134A1 - Pièce de dispositif à plasma et son procédé de fabrication - Google Patents

Pièce de dispositif à plasma et son procédé de fabrication Download PDF

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WO2015080134A1
WO2015080134A1 PCT/JP2014/081189 JP2014081189W WO2015080134A1 WO 2015080134 A1 WO2015080134 A1 WO 2015080134A1 JP 2014081189 W JP2014081189 W JP 2014081189W WO 2015080134 A1 WO2015080134 A1 WO 2015080134A1
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Prior art keywords
oxide
yttrium oxide
particles
lanthanoid element
plasma device
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PCT/JP2014/081189
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English (en)
Japanese (ja)
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佐藤　道雄
高志 日野
仁 中谷
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株式会社東芝
東芝マテリアル株式会社
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Priority to KR1020167013892A priority Critical patent/KR101807444B1/ko
Priority to JP2015550947A priority patent/JP6526568B2/ja
Publication of WO2015080134A1 publication Critical patent/WO2015080134A1/fr

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    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5045—Rare-earth oxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
    • H01L21/02312—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a gas or vapour
    • H01L21/02315—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a gas or vapour treatment by exposure to a plasma
    • 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

Definitions

  • the present invention relates to a plasma device component coated with an oxide film, which has excellent corrosion resistance against halogen-based corrosive gas and plasma and can be suitably used for plasma device components for semiconductor and liquid crystal production.
  • ceramic materials such as alumina (aluminum oxide), aluminum nitride, yttria (yttrium oxide), and YAG are widely used as constituent materials of components exposed to halogen plasma in the above-described processes.
  • the base material is made of a metal or a ceramic provided with a metal electrode, and the outermost surface on the base material has 5% by weight or more and less than 60% by weight of tungsten or molybdenum with respect to yttrium oxide. It is described that, by dispersing and forming an yttrium oxide plasma sprayed coating having a porosity of 5% or less, a plasma device component (electrostatic chuck) having a stable low volume resistivity dielectric layer can be obtained. ing.
  • Patent Document 2 a dielectric layer composed of a main component of aluminum oxide and a resistivity adjusting component containing titanium oxide and a group 5A metal is formed on the surface of a ceramic substrate such as aluminum oxide by an atmospheric plasma spraying method.
  • a plasma device component electrostatic chuck
  • a stable dielectric layer having a low volume resistivity can be obtained.
  • coating films such as yttrium oxide and aluminum oxide formed by the above thermal spraying method are formed by depositing raw material powders such as yttrium oxide and aluminum oxide in a molten state, so that the molten particles are rapidly solidified by the thermal spray heat source.
  • a large number of microcracks are generated in the particles deposited in a flat state, and further, strains generated by rapid solidification remain in the respective flat particles to form a film.
  • active radicals generated by plasma discharge are irradiated to a film such as yttrium oxide or aluminum oxide, the active radicals attack the microcracks, and the cracks develop, and further, the internal strain is released. Further, there is a problem that cracks propagate and the sprayed coating is lost to cause generation of particles.
  • plasma device parts having ceramic sprayed coatings have a structure in which flat particles are deposited, so that irregular surface irregularities remain on the surface even when polishing finish is performed, and dielectrics are formed during processing such as etching. There is a concern that the particles present on the surface of the layer are shed and particles are generated due to these.
  • the coating film such as yttrium oxide or aluminum oxide formed by the thermal spraying process is a deposited film in the molten state, and therefore tends to be a source of particles and causes a decrease in product yield. Forming is prone to problems.
  • the thermal spray coating is deposited on the surface that has been subjected to a blasting process in which abrasive grains and the like are sprayed onto the surface of the base material together with the high-pressure grains. Residual pieces of blasting material (abrasive grains) may be present, or a fragile fracture layer may be formed by blasting on the part surface. Since the thermal spray coating is deposited on the surface of the component in this way, the thermal stress generated by the temperature change caused by the plasma discharge causes the stress to act on the interface between the component and the thermal spray coating, and the film is likely to peel off together with the thermal spray coating. .
  • the life of the thermal spray coating is a factor greatly influenced by the conditions of the blast treatment in addition to the configuration of the thermal spray coating itself.
  • the particle diameter of the yttrium oxide powder supplied as a raw material is as large as about 10 to 45 ⁇ m, pores (voids) are generated up to about 15% in the formed sprayed coating, and the surface of the sprayed surface
  • the roughness becomes as coarse as about 6 to 10 ⁇ m on the basis of the arithmetic average roughness Ra, and there is a problem that a long time is required for planarization by the polishing process.
  • plasma etching proceeds through the pores. Further, if the surface roughness is large, the plasma discharge is struck by being concentrated on the convex portion of the sprayed surface.
  • the thermal spray coating is brittle due to surface defects, so the amount of particles generated due to wear of the thermal spray coating increases, and the service life of plasma equipment components decreases. There was also a problem that invited.
  • the wiring width is being reduced (for example, 24 nm and 19 nm).
  • the wiring width is being reduced (for example, 24 nm and 19 nm).
  • ultrafine particles (fine particles) having a diameter of, for example, about 40 nm are mixed, the cause of wiring failure (disconnection) or device failure (short circuit) is caused.
  • the present invention has been made in order to solve the above-described conventional problems, and improves the plasma resistance and corrosion resistance of the coating itself during the etching process, thereby stably and effectively suppressing the generation of particles, and cleaning the apparatus and parts. It is possible to prevent contamination due to impurities by suppressing the decrease in productivity due to replacement, etc., and increasing the cost of etching and film formation, as well as preventing film peeling and effectively suppressing the generation of fine particles. It is an object of the present invention to provide a plasma device component and a method for manufacturing the plasma device component that do not cause damage such as corrosion or deformation to a member by chemical treatment or blast treatment in a regenerating process.
  • a component for a plasma apparatus having an yttrium oxide film formed by the shock sintering method of the present invention is a lanthanoid selected from 1 to 8% by mass of La, Ce, Sm, Dy, Gd, Er, and Yb in an yttrium oxide film. It has an yttrium oxide film containing at least one kind of system element in terms of oxide, the thickness of the film is 10 ⁇ m or more, the density of the film is 90% or more, and the unit area of the film is 20 ⁇ m ⁇ 20 ⁇ m
  • the area ratio of particles in which existing grain boundaries can be confirmed is 0 to 80%, while the area ratio of particles in which no grain boundaries can be confirmed is 20 to 100%.
  • the yttrium oxide coating containing the oxide of the lanthanoid element has a thickness of 10 to 200 ⁇ m, and the coating density is preferably 99% or more and 100% or less. It is preferable that the oxide particles of the yttrium oxide and the lanthanoid element include fine particles having a particle size of 1 ⁇ m or less, and the yttrium oxide particles that can confirm the grain boundary have an average particle size of 2 ⁇ m or less. The average particle size of the oxide particles of yttrium oxide and lanthanoid elements is preferably 5 ⁇ m or less.
  • the ratio (Im / Ic) of the monoclinic strongest peak Im to the cubic strongest peak Ic was 0.2 to 0.6.
  • the yttrium oxide film containing the oxide of the lanthanoid element has a surface roughness Ra of 0.5 ⁇ m or less by polishing treatment.
  • a method for manufacturing a plasma device component in which an yttrium oxide film containing an oxide of a lanthanoid element is formed by the shock sintering method of the present invention includes a step of supplying a slurry containing oxide particles to a combustion flame, and a yttrium oxide particle And a step of injecting the lanthanoid element oxide particles onto the substrate at an injection speed of 400 to 1000 m / sec.
  • the average particle size of the yttrium oxide particles and the lanthanoid element oxide particles is preferably 0.05 to 5 ⁇ m.
  • the film thickness of the yttrium oxide film containing an oxide of a lanthanoid element is preferably 10 ⁇ m or more.
  • a slurry containing yttrium oxide particles and lanthanoid-based element oxide particles is preferably supplied to the center of the combustion flame.
  • an oxide of a lanthanum element using an impact sintering method deposited without melting a supply powder containing fine particles having an average particle size of 5 ⁇ m or less and a particle size of 1 ⁇ m or less at the time of coating formation
  • a supply powder containing fine particles having an average particle size of 5 ⁇ m or less and a particle size of 1 ⁇ m or less at the time of coating formation
  • fine particles having a particle size of 1 ⁇ m or less are also deposited, so that microvoids can be reduced and surface defects can be reduced.
  • An yttrium oxide film containing an oxide of a lanthanoid element such as La, Ce, Sm, Dy, Gd, Er, or Yb in the film achieves higher density and smoother surface than the yttrium oxide single film. Therefore, the internal defects of the coating can be reduced. This improves the densification of the film compared to a film composed of yttrium oxide alone, and increases the stability of the crystal structure of the oxide constituting the film, thereby improving the chemical stability of the film. It is possible to improve plasma resistance and corrosion resistance.
  • the lanthanoid element can be suitably used as a single metal, an oxide, or a complex oxide with Y 2 O 3 .
  • An oxide or a complex oxide is preferable. If it is an oxide or a complex oxide, it becomes possible to improve corrosion resistance more.
  • the plasma resistance of the component can be improved, and the amount of particles generated and the amount of impurity contamination can be suppressed.
  • the chemical treatment or blast treatment in the regeneration treatment does not damage the member such as corrosion or deformation, the number of times of cleaning the device or replacing parts can be greatly reduced.
  • the reduction in the amount of generated particles greatly contributes to the improvement of the yield of various thin films to be subjected to plasma etching, as well as elements and components using the thin films.
  • the reduction in the number of device cleanings and part replacements greatly contributes to the improvement of productivity and the reduction of etching costs and film formation costs.
  • the present invention provides a plasma device component that can be applied to the manufacture of highly integrated semiconductor devices and that can reduce the cost of etching and film formation by improving the operating rate, and a method for manufacturing the same. be able to.
  • a component for a plasma apparatus having an yttrium oxide film formed by the shock sintering method of the present invention is a lanthanoid selected from 1 to 8% by mass of La, Ce, Sm, Dy, Gd, Er, and Yb in an yttrium oxide film.
  • the area ratio is 0 to 80%, while the area ratio of particles in which no grain boundary can be confirmed is 20 to 100%.
  • FIG. 1 shows an example of the structure of an electrostatic chuck component as a plasma device component according to the present invention.
  • reference numeral 1 denotes a plasma device component
  • 2 denotes an yttrium oxide coating containing an oxide of a lanthanoid element
  • 3 denotes a substrate.
  • Yttrium oxide alone has strong resistance to chlorine-based plasma attack, fluorine-based plasma attack, and radical attack (for example, active F radical and Cl radical), but has corrosion resistance La, Ce, Sm, Dy, Gd, Er,
  • the corrosion resistance can be further improved.
  • lanthanoid-based oxide particles combine yttrium oxide particles to improve the grain boundary strength, exhibit an effect of eliminating the particle step in the polishing finish, and adjust the volume resistivity of the coating.
  • the amount of the lanthanoid element oxide added is less than 1% by mass, the above-mentioned effect is not sufficiently exhibited.
  • the addition amount exceeds 8% by mass, the grain boundary layer becomes thick, leading to a decrease in the film strength and a significant particle step.
  • a more preferable addition amount is 2 to 6% by mass.
  • the yttrium oxide film containing an oxide of a lanthanoid element has yttrium oxide particles containing an oxide of a lanthanoid element.
  • a film is formed by a general thermal spraying method, the film is formed in a state where yttrium oxide particles containing an oxide of a lanthanoid element are dissolved. Therefore, yttrium oxide particles containing an oxide of a lanthanoid element are flat.
  • the area ratio of particles in which the grain boundaries existing in the unit area 20 ⁇ m ⁇ 20 ⁇ m of the coating structure can be confirmed is 0 to 80%, while the area ratio of particles in which the grain boundaries cannot be confirmed is 20 to 100%. It is characterized by being.
  • the yttrium oxide particles containing an oxide of a lanthanoid element that can confirm the above grain boundary can be confirmed by an enlarged photograph.
  • an enlarged photograph of 5000 times is taken with a scanning electron micrograph.
  • FIG. 2 shows an example (enlarged photo) showing an example of an yttrium oxide coating containing an oxide of a lanthanoid element.
  • reference numeral 4 is a particle whose grain boundary cannot be confirmed
  • 5 is a particle whose grain boundary can be confirmed.
  • the grain which can confirm a grain boundary can confirm the grain boundary of each grain by the difference in contrast.
  • particles whose grain boundaries cannot be confirmed cannot be confirmed by adjoining particles to each other.
  • the unit area of the coating structure was 20 ⁇ m ⁇ 20 ⁇ m. Further, this unit area is measured at three arbitrary points, and the average value is defined as the area ratio of “particles that can confirm grain boundaries” and “particles that contain oxides of lanthanoid elements whose grain boundaries cannot be confirmed”. In FIG. 2, a particle group of “particles whose grain boundaries can be confirmed” and a particle group of “particles whose grain boundaries cannot be confirmed” are mixed.
  • the impact sintering method is a coating method in which particles are jetted by a combustion flame, and the particles collide at a high speed, and a film is formed by sinter bonding with the crushing heat of the particles caused by the collision. is there. Therefore, the yttrium oxide particles in the yttrium oxide film containing the oxide of the lanthanoid element tend to form a crushed film rather than the particle shape of the raw material powder.
  • the yttrium oxide particles containing the lanthanoid element oxide are melted by controlling the injection speed of the yttrium oxide particles containing the lanthanoid element oxide to a high speed and accelerating to a speed higher than the critical speed at which the particles start to deposit.
  • a yttrium oxide film containing an oxide of a lanthanoid element having a high film density and substantially maintaining the particle shape of the raw material powder Since the impact sintering method enables high-speed injection, it is easy to obtain a structure in which “particles whose grain boundaries can be confirmed” and “particles whose grain boundaries cannot be confirmed” are mixed.
  • the area ratio of “particles whose grain boundaries can be confirmed” is 0 to 80%, It is important that the area ratio of “particles whose grain boundaries cannot be confirmed” is 20 to 100%.
  • the impact sintering method is a film forming method in which yttrium oxide particles containing an oxide of a lanthanoid-based element are jetted at high speed, and the particles are deposited by destructive heat when colliding with a substrate.
  • yttrium oxide particles containing the lanthanoid element oxide are bonded by heat at the time of deposition by the fracture heat, yttrium oxide particles containing the lanthanoid element oxide whose grain boundary cannot be confirmed are formed.
  • the raw material powder since the raw material powder is not melted and sprayed by spraying at a high speed by spraying, it can be deposited while maintaining the powder shape of the yttrium oxide particles containing the oxide of the lanthanoid element as the raw material powder. As a result, no stress is generated inside the film, and a dense and strong coating can be formed.
  • the area ratio of “particles whose grain boundaries can be confirmed” is preferably 0 to 50%. This means that the area ratio of “particles whose grain boundaries cannot be confirmed” is preferably in the range of 50 to 100%.
  • the thickness of the yttrium oxide coating containing the oxide of the lanthanoid element needs to be 10 ⁇ m or more. If the film thickness is less than 10 ⁇ m, the effect of providing an yttrium oxide film containing an oxide of a lanthanoid element cannot be obtained sufficiently, and on the contrary, the film may be peeled off.
  • the upper limit of the thickness of the yttrium oxide film containing the oxide of the lanthanoid element is not particularly limited, but if it is excessively thick, no further effect can be obtained, and the cost increases. Therefore, the thickness of the yttrium oxide film containing the oxide of the lanthanoid element is in the range of 10 to 200 ⁇ m, and more preferably in the range of 50 to 150 ⁇ m.
  • the coating density needs to be 90% or more.
  • the density of the coating is a term opposite to the porosity, and the density of 90% or more has the same meaning as the porosity of 10% or less.
  • an yttrium oxide film containing an oxide of a lanthanoid element is taken in a film thickness direction, a cross-sectional structure photograph is taken 500 times magnified by an optical microscope, and the area ratio of pores reflected therein is calculated.
  • “Membrane density (%) 100 ⁇ pore area ratio”
  • the film density is calculated by the following formula. In calculating the coating density, an area of a unit area 200 ⁇ m ⁇ 200 ⁇ m of the tissue is analyzed. In addition, when the thickness of a film is thin, it shall measure in several places until the total unit area will be 200 micrometers x 200 micrometers.
  • the film density is 90% or more, more preferably 95% or more, and further preferably 99% or more and 100% or less.
  • the surface roughness of the yttrium oxide film containing the oxide of the lanthanoid element is preferably set to Ra 0.5 ⁇ m or less by polishing treatment.
  • the surface roughness after the polishing process is Ra 0.5 ⁇ m or less, the wafer comes into close contact with the dielectric layer and the etching uniformity is improved.
  • the surface roughness after the polishing process exceeds Ra 0.5 ⁇ m, the wafer is deformed, the adhesion is lowered, the etching property becomes non-uniform, and particles are liable to be generated.
  • the average particle diameter of yttrium oxide particles containing an oxide of a lanthanoid element that can confirm a grain boundary is 2 ⁇ m or less, and the entire lanthanoid element including yttrium oxide particles containing an oxide of a lanthanum element that cannot confirm a grain boundary. It is preferable that the average particle diameter of the yttrium oxide particles containing the oxide is 5 ⁇ m or less.
  • the yttrium oxide powder containing an oxide of a lanthanoid element as a raw material powder using an impact sintering method preferably has an average particle size in the range of 0.05 to 5 ⁇ m.
  • the average particle size of the yttrium oxide particles containing the oxide of the lanthanoid element as the raw material powder exceeds 5 ⁇ m, when the particles collide with each other, it becomes difficult to form a coating without being crushed, and the blasting action of the particles themselves May damage the coating and cause cracks.
  • the yttrium oxide particles containing an oxide of a lanthanoid element are 5 ⁇ m or less, crushing proceeds moderately when the fine particles collide, and particle bonding is promoted by heat generated by crushing, so that a film is easily formed.
  • the formed film has a high bonding force between particles, wear due to plasma attack and radical attack is reduced, the amount of generated particles is reduced, and plasma resistance is improved.
  • a more preferable value of the particle diameter of the particles is 0.05 ⁇ m or more and 3 ⁇ m or less.
  • the particle diameter is less than 0.05 ⁇ m, the particles are less likely to be crushed and formed as a film, but the film has a low density. Since the plasma resistance and the corrosion resistance are lowered, the application range of the fine particle diameter is preferably 0.05 to 5 ⁇ m. However, if the fine particles of less than 0.05 ⁇ m are less than 5% of the total yttrium oxide particles containing the oxide of the lanthanoid element, the film formation does not deteriorate, so a powder containing fine particles of less than 0.05 ⁇ m is used. It doesn't matter.
  • the average particle diameter is obtained using an enlarged photograph as shown in FIG.
  • the particle whose grain boundary can be confirmed has the longest diagonal line as the particle size in each particle shown in the photograph.
  • Particles for which grain boundaries cannot be confirmed are determined by using the hypothetical circle of each particle as the diameter. This operation is performed for 50 particles each, for a total of 100 particles, and the average value is defined as the average particle size.
  • the ratio of the monoclinic strongest peak Im to the strongest peak Ic of cubic is preferably 0.2 to 0.6.
  • the XRD analysis is performed by the 2 ⁇ method, a Cu target, a tube voltage of 40 kV, and a tube current of 40 mA.
  • the strongest peak of the cubic crystal is detected between 28 and 30 °, while the strongest peak of the monoclinic crystal is detected between 30 and 33 °.
  • commercially available yttrium oxide particles are cubic. It is preferable that the monoclinic crystal is increased because it changes to monoclinic crystal due to the heat of fracture of the impact sintering method, and when the monoclinic crystal is increased, the plasma resistance is improved.
  • the method of manufacturing a plasma device component in which an yttrium oxide film containing an oxide of a lanthanoid element is formed by the shock sintering method of the present invention includes a slurry containing yttrium oxide particles containing an oxide of a lanthanoid element in a combustion flame. And a step of spraying yttrium oxide particles containing an oxide of a lanthanoid-based element onto a substrate at an injection speed of 400 to 1000 m / sec.
  • the average particle diameter of the yttrium oxide particles containing the oxide of the lanthanoid element is preferably 0.05 to 5 ⁇ m.
  • the film thickness of the yttrium oxide particles containing the oxide of the lanthanoid element is preferably 10 ⁇ m or more.
  • the slurry containing yttrium oxide particles containing an oxide of a lanthanoid element is preferably supplied to the center of the combustion flame.
  • the impact sintering method is a film forming method in which a slurry containing yttrium oxide particles containing an oxide of a lanthanoid element is supplied into a combustion flame, and yttrium oxide particles containing an oxide of a lanthanoid element are injected at high speed. .
  • the film forming apparatus for performing the impact sintering method includes a combustion source supply port for supplying a combustion source and a combustion chamber connected thereto. By burning the combustion source in the combustion chamber, a combustion flame is generated at the combustion flame opening.
  • a slurry supply port is disposed in the vicinity of the combustion flame, and the yttrium oxide particle slurry containing the oxide of the lanthanoid element supplied from the slurry supply is injected from the combustion flame to the base material through the nozzle. It will be filmed.
  • combustion source oxygen, acetylene, kerosene or the like is used, and two or more kinds may be used as necessary. Further, the combustion conditions such as the blending ratio of the combustion source and the amount of cooling gas input are adjusted so that the temperature of the combustion flame is less than the boiling point of the yttrium oxide particles containing the oxide of the lanthanoid element to be formed.
  • the yttrium oxide particles containing oxides of the lanthanoid elements supplied as a slurry evaporate, decompose or melt, even if high-speed injection, do not accumulate, Or even if it deposits, it will become the form similar to thermal spraying.
  • the spray rate of yttrium oxide particles containing an oxide of a lanthanoid element may be in the range of 400 m / sec to 1000 m / sec. preferable. If the spray speed is as low as less than 400 m / sec, the pulverization when the particles collide may be insufficient and a film having a high film density may not be obtained. On the other hand, when the injection speed exceeds 1000 m / sec, the impact force becomes excessive, the blast effect due to the yttrium oxide particles containing the oxide of the lanthanoid element is likely to occur, and the intended film is difficult to obtain.
  • the yttrium oxide particle slurry containing the oxide of the lanthanoid element is introduced into the slurry supply port, it is preferable to supply the slurry so that the slurry is injected into the center of the combustion flame.
  • the injection speed will not be stable.
  • Yttrium oxide particles containing oxides of some lanthanoid elements are injected outside the combustion flame, and some are injected after reaching the center. Even with the same flame flame, the combustion temperature differs slightly between the outside and inside. By forming the film under the same temperature conditions and the same injection speed as much as possible, it is possible to control the structure composed of “particles whose grain boundaries can be confirmed” and “particles whose grain boundaries cannot be confirmed”.
  • the impact sintering method is a coating method in which particles are jetted by a combustion flame, and the particles collide at a high speed, and a film is formed by sinter bonding with the crushing heat of the particles caused by the collision. is there. For this reason, yttrium oxide particles containing an oxide of a lanthanoid element in the coating tend to form a coating having a crushed shape rather than the particle shape of the raw material powder.
  • yttrium oxide particles containing lanthanoid element oxides are not melted.
  • An yttrium oxide film containing an oxide of a lanthanum element having a high film density can be obtained. Since the impact sintering method enables high-speed injection, it is easy to obtain “particles whose grain boundaries cannot be confirmed”.
  • An yttrium oxide coating film containing an oxide of a lanthanoid element in which the area ratio of particles in which grain boundaries can be confirmed as in the present invention is 0 to 80%, while the area ratio of particles in which grain boundaries cannot be confirmed is 20 to 100% Can be obtained efficiently.
  • the impact sintering method uses a combustion flame flame to inject yttrium oxide particles containing an oxide of a lanthanoid element at high speed, and sinter-bond by using the heat of fracture of the particles at the time of collision. It is a method to make.
  • the injection distance L is 100 to 400 mm.
  • the spray distance L is less than 100 mm, it is difficult to obtain a coating in which the yttrium oxide particles containing the oxide of the lanthanoid element are sintered without being crushed because the distance is too short.
  • the spray distance L exceeds 400 mm, the impact force is weakened because it is too far away, and it is difficult to obtain a target yttrium oxide film containing an oxide of a lanthanoid element.
  • the injection distance L is 100 to 200 mm.
  • the yttrium oxide particle slurry containing the lanthanoid element oxide is preferably a slurry containing yttrium oxide particles containing the lanthanoid element oxide having an average particle size of 0.05 to 5 ⁇ m as a raw material powder.
  • the solvent for slurrying is preferably a solvent that is relatively volatile, such as methyl alcohol or ethyl alcohol.
  • the yttrium oxide particles containing the oxide of the lanthanoid element are mixed with a solvent after being sufficiently pulverized and free of coarse particles.
  • coarse particles having a particle size of 20 ⁇ m or more, it is difficult to obtain a uniform film.
  • the yttrium oxide particles in the slurry are preferably 30 to 80 vol%.
  • the crystal structure of the raw material powder (yttrium oxide particle slurry containing the lanthanoid element oxide) is changed to a monoclinic crystal, and the yttrium oxide film containing the lanthanoid element oxide is formed.
  • yttrium oxide is cubic at room temperature.
  • the crystal structure changes when exposed to high temperatures such as a combustion flame, but the impact sintering method can be sprayed at high speed, so it changes to a monoclinic crystal and contains an oxide of a lanthanoid element with high plasma resistance.
  • the plasma resistance of the parts for the plasma etching apparatus is remarkably improved, and it is possible to reduce particles, reduce impurity contamination, and extend the service life of the parts. For this reason, if it is a plasma etching apparatus using such a part for plasma etching apparatuses, it will become possible to generate particles and reduce the number of parts replacement during the plasma etching process.
  • the generation of particles due to the peeling of the yttrium oxide film deposited on the parts can be effectively suppressed, and the number of times of device cleaning and part replacement can be greatly reduced.
  • the reduction in the amount of generated particles greatly contributes to the improvement of the yield of various thin films that are etched and formed by a semiconductor manufacturing apparatus, and further, the elements and components using the thin films.
  • extending the service life of parts by reducing the number of times of device cleaning and parts replacement and eliminating the need for blasting will greatly contribute to the improvement of productivity and the reduction of etching costs.
  • Plasma is formed by adding various oxide ceramics to yttrium oxide under the conditions shown in Table 1 on an alumina substrate (300 mm x 3 mm) by an impact sintering method using a combustion frame type injection device. It was set as equipment parts.
  • the solvent of yttrium oxide particles and other oxide particle slurries was ethyl alcohol.
  • the raw material powder used was high-purity oxide particles having a purity of 99.9% or more. Further, Y 2 O 3 particles as the raw material powder is cubic, using raw material powder no coarse particles of more than 10 ⁇ m by sufficient grinding and sieving.
  • Comparative Example 1 is a film formed by plasma spraying using yttrium oxide powder having an average particle size of 14 ⁇ m as a raw material.
  • the film density was obtained from the ratio of pores appearing in an enlarged photograph (500 times) so that the total unit area of the film cross section was 200 ⁇ m ⁇ 200 ⁇ m.
  • the area ratio between the particles where the grain boundaries can be confirmed and the particles where the grain boundaries cannot be confirmed is obtained by taking an enlarged photograph (magnification 5000 times) of a unit area of 20 ⁇ m ⁇ 20 ⁇ m on the coating surface to understand the grain boundary of one yttrium oxide particle.
  • the area ratio was determined as “particles whose grain boundaries can be confirmed” and those whose grain boundaries are not bonded and understood as “particles whose grain boundaries cannot be confirmed”.
  • the crystal structure was investigated by XRD analysis.
  • XRD analysis was performed using a Cu target under the conditions of a tube voltage of 40 kV and a tube current of 40 mA, and the ratio of the strongest peak Im of the monoclinic crystal to the strongest peak Ic of the cubic crystal (Im / Ic) was investigated. The results are shown in Table 2 below.
  • the yttrium oxide film containing the oxide of the lanthanoid element according to each example has a high film density, and the ratio (area ratio) of “particles whose grain boundaries can be confirmed” is 0. It was in the range of ⁇ 80%. Moreover, it became the particle
  • the surface roughness Ra of the yttrium oxide coating in each of Examples 1 to 8 was 0.5 ⁇ m or less.
  • the surface roughness Ra of the film in Comparative Example 1 was 3.1 ⁇ m.
  • the components for the plasma etching apparatus according to each example and comparative example were placed in the plasma etching apparatus and exposed to a mixed etching gas of CF 4 (50 sccm) + O 2 (20 sccm) + Ar (50 sccm). After setting the inside of the etching chamber to 10 mTorr and continuously operating for 2 hours at an output of 300 W (bias 100 W), as an evaluation of the peeling for each yttrium oxide coating, It was measured.
  • each yttrium oxide film was measured at room temperature (25 ° C.) by a four-terminal method (conforming to JIS K 7194), and as a result, it was in the range of 1.2 to 1.5 ⁇ 10 12 ⁇ ⁇ cm.
  • particles generated from the component can be stably and effectively prevented. Further, since the corrosion of the coating film against the active radicals of the corrosive gas is suppressed, it is possible to prevent the generation of particles from the coating film, and it is possible to suppress the generation of particles by reducing the corrosion products and preventing the falling off. Therefore, it is possible to reduce the number of times of cleaning the plasma device parts and replacing the parts.

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Abstract

La présente invention porte sur : une pièce de dispositif à plasma ayant un film d'oxyde d'yttrium contenant des microparticules formées par frittage par impact ayant un diamètre inférieur ou égal à 1 µm, la pièce de dispositif à plasma étant caractérisée en ce que le film d'oxyde d'yttrium comprend un film contenant 1-8 % en masse d'un oxyde d'un élément lanthanoïde choisi parmi La, Ce, Sm, Dy, Gd, Er et Yb, l'épaisseur du film est d'au moins 10 µm, la densité du film est d'au moins 90 % et le rapport de surface des particules, présentes dans une surface unitaire de 20 µm × 20 µm du film, pour lesquelles les joints de grains sont visibles est de 0- 80 % alors que le rapport de surface de particules pour lesquelles les joints de grains sont fusionnés est de 20-100 %; et son procédé de fabrication. Ladite configuration permet d'obtenir : une pièce de dispositif à plasma avec laquelle il est possible de limiter de façon stable et de façon efficace l'apparition de particules pendant le processus à plasma, de limiter la réduction de productivité et le coût accru de gravure et de formation de film et d'empêcher la contamination de produit par des impuretés par limitation de l'apparition de microparticules; et un procédé de fabrication s'y rapportant.
PCT/JP2014/081189 2013-11-29 2014-11-26 Pièce de dispositif à plasma et son procédé de fabrication WO2015080134A1 (fr)

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KR102371936B1 (ko) * 2019-12-04 2022-03-08 한국세라믹기술원 내플라즈마 침식성 및 기계적 특성이 우수한 반도체 부품의 코팅방법
KR102209860B1 (ko) * 2020-10-20 2021-01-29 와이엠씨 주식회사 디스플레이 패널 제조에 사용되는 플라즈마 처리장치용 내부부품의 표면처리방법
KR102439674B1 (ko) * 2022-07-25 2022-09-02 주식회사 코닉스 내플라즈마성이 향상된 알루미나 세라믹 소재 및 내플라즈마성이 향상된 알루미나 세라믹 소재의 제조 장치

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JPH1045461A (ja) * 1996-07-31 1998-02-17 Kyocera Corp 耐食性部材
JP2010064937A (ja) * 2008-09-12 2010-03-25 Covalent Materials Corp プラズマ処理装置用セラミックス
JP2012191200A (ja) * 2011-02-25 2012-10-04 Toshiba Corp プラズマ処理装置
WO2013176168A1 (fr) * 2012-05-22 2013-11-28 株式会社東芝 Élément pour appareil de traitement par plasma et procédé de fabrication d'un élément pour appareil de traitement par plasma

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JP4780932B2 (ja) * 2004-05-25 2011-09-28 京セラ株式会社 耐食性部材とその製造方法および半導体・液晶製造装置用部材
JP5284227B2 (ja) 2009-09-07 2013-09-11 日本特殊陶業株式会社 静電チャック及び静電チャックの製造方法

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JPH1045461A (ja) * 1996-07-31 1998-02-17 Kyocera Corp 耐食性部材
JP2010064937A (ja) * 2008-09-12 2010-03-25 Covalent Materials Corp プラズマ処理装置用セラミックス
JP2012191200A (ja) * 2011-02-25 2012-10-04 Toshiba Corp プラズマ処理装置
WO2013176168A1 (fr) * 2012-05-22 2013-11-28 株式会社東芝 Élément pour appareil de traitement par plasma et procédé de fabrication d'un élément pour appareil de traitement par plasma

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