JPWO2010027073A1 - Semiconductor manufacturing equipment parts and semiconductor manufacturing equipment - Google Patents

Abstract

A component for a semiconductor manufacturing apparatus and a component for a compound semiconductor device, each comprising a component main body and a thermal spray coating formed on the surface of the component main body by spraying nitride particles, wherein the nitride particles in the thermal spray coating are not yet formed. A component for a semiconductor manufacturing apparatus and a component for a compound semiconductor manufacturing apparatus are characterized by being deposited by melting 90 mass% or more. In sprayed coatings formed by rapidly solidifying molten particles, many microcracks are generated in the particles, and the strain remains, so particles are generated as dust from the sprayed coating of parts in the plasma discharge process. To do. ADVANTAGE OF THE INVENTION According to this invention, the components for semiconductor manufacturing apparatuses and the components for compound semiconductor manufacturing apparatuses which suppressed the generation | occurrence | production of the said dust stably and effectively can be provided.

Description

  The present invention relates to a component for a semiconductor manufacturing apparatus, a component for manufacturing a compound semiconductor, a semiconductor manufacturing apparatus, and a compound semiconductor manufacturing apparatus suitable for an apparatus for forming fine wiring using plasma discharge, such as a plasma etching apparatus, a plasma CVD apparatus, and a sputtering apparatus. About.

  The fine wiring in semiconductor device manufacture and compound semiconductor device manufacture is formed by using a film formation method using a sputtering device or a CVD device and a technique of isotropic etching and anisotropic etching using an etching device. In these apparatuses, plasma discharge is used for improving the film forming speed and etching property.

  Here, a plasma etching apparatus will be described as a typical example of a semiconductor manufacturing apparatus using plasma discharge. In a manufacturing process of a semiconductor manufacturing apparatus, a method is known in which plasma gas is used for fine etching of Si and dry etching processes of various thin films such as an insulating film, an electrode film, and a wiring film formed on a substrate. . Specifically, a fluorine (F) system or a chlorine (Cl) system that is a gas between an upper electrode disposed in a chamber of a dry etching apparatus and a substrate mounted on a lower electrode surface disposed opposite to the upper electrode. Plasma gas is discharged between the electrodes to generate fluorine or chlorine plasma, and the thin film formed on the substrate is dry etched with active ions or radicals generated in the plasma. The method to be applied is applied.

  The product formed by etching from the thin film on the substrate by dry etching using fluorine-based or chlorine-based plasma becomes a gas state and is discharged from the chamber to the outside by the exhaust pump. In addition, since a part of the product is in a solid state and is deposited in the chamber to become an adhesion film, a gas different from the fluorine-based or chlorine-based plasma gas used for the dry etching is used for the purpose of removing the adhesion film. A process is employed in which dry etching is performed under conditions to discharge a product adhered in the chamber out of the chamber.

  However, when a fluorocarbon etching product is generated and deposited, the product does not react completely with fluorine or chlorine plasma, so the product remains in the chamber and the deposited film peels off. Then, it mixes on the substrate, leading to pattern defects and yield reduction.

For this reason, in the dry etching apparatus, a thermal spray coating made of yttrium oxide (Y ₂ O ₃ ) or aluminum oxide (Al ₂ O ₃ ) having high plasma resistance and corrosion resistance is formed on the parts irradiated with plasma. However, yttrium oxide or aluminum oxide is used to suppress generation of products and prevent damage due to plasma attack.

  However, the coating of yttrium oxide or aluminum oxide formed by thermal spraying is formed by depositing raw material powder of yttrium oxide or aluminum oxide in a molten state, so that the molten particles are rapidly solidified by a plasma heat source and adhered. At this time, a large number of microcracks are generated in the particles deposited in a flat state, and further, a strain formed by rapid solidification remains in each flat particle, and a coating is formed. When an active radical generated by plasma discharge is irradiated to an yttrium oxide film or an aluminum oxide film in such a state, the active radical attacks the microcrack to develop the crack, There is a problem in that cracks propagate and the sprayed coating is lost to cause generation of particles.

  Further, with the progress of cracks in the thermal spray coating, there is a problem that the deposit generated thereon is peeled off, which induces generation of particles.

  As described above, the yttrium oxide film or aluminum oxide formed by the thermal spraying process is a deposited film of particles in the molten state, and therefore tends to be a source of particles and causes a reduction in product yield. The formation tends to cause problems (see Patent Document 1).

Furthermore, when forming a sprayed coating on a component, the sprayed 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 substrate surface together with a high-pressure fluid. Residual pieces of material (abrasive grains) may exist, or a crushed layer may be formed by blasting on the part surface. Since the sprayed coating is deposited on the surface of the component as described above, the thermal film stress due to the temperature change caused by the plasma discharge causes the stress to act on the interface between the component and the sprayed coating, and the film is easily peeled off together with the sprayed coating. In particular, when the blasting pressure or the abrasive grain size is increased, the occurrence of film peeling becomes significant. For this reason, 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.
JP 2002-313780 A

DISCLOSURE OF THE INVENTION The present invention is capable of stably and effectively suppressing the generation of fine dust generated from parts, and for semiconductor manufacturing equipment parts and compound semiconductor manufacturing equipment capable of preventing contamination by impurities from the parts. An object is to provide a component and semiconductor manufacturing apparatus and a compound semiconductor manufacturing apparatus.

  As described above, in the measures for preventing the separation of deposits in the components of the dry etching apparatus, defects exist in the coating of yttrium oxide and aluminum oxide formed by the thermal spraying method and at the interface with the components. Even with yttrium oxide and aluminum oxide, which have corrosion resistance, it is not possible to sufficiently suppress the life of the coating film and to prevent the deposits attached to the surface of the component from being peeled off. There is. When the deposits are peeled off, the amount of generated particles increases abruptly. Therefore, it is necessary to frequently clean the apparatus and replace parts, resulting in a decrease in productivity and an increase in film formation cost.

  In the case of plasma spraying, since the particle diameter of the oxide powder as the supply powder is as large as about 10 to 45 μm, pores (voids) are generated up to about 15% in the formed sprayed coating and the surface of the sprayed surface is rough. The average roughness Ra is about 6 to 10 μm. When a plasma etching apparatus component having such a thermal spray coating is used, 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. In addition to the concentration of plasma attacks on internal defects in this way, the thermal spray coating becomes 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 parts and equipment is reduced. Invite.

  In other words, in dry etching equipment that requires plasma resistance and corrosion resistance, even with yttrium oxide coatings and aluminum oxides, the antifouling measures for deposits do not function completely due to coating defects, resulting in decreased productivity and etching costs. And so on.

  Further, in recent semiconductor elements, in order to achieve a high degree of integration, the wiring width has been reduced (for example, 0.18 μm, 0.13 μm, and further 0.09 μm or less). In such a narrowed wiring and an element having the wiring, even if extremely fine particles (micro particles) having a diameter of about 0.2 μm are mixed, for example, wiring defects and element defects are caused. It is strongly desired to further suppress the generation of fine particles due to the device components.

  The present invention has been made to cope with such problems, and aluminum nitride (AlN) having plasma resistance and corrosion resistance more than yttrium oxide and aluminum oxide is applied to parts for semiconductor manufacturing equipment and compound semiconductor manufacturing equipment. In addition, AlN powder is deposited without causing internal defects, and it is possible to stably and effectively prevent peeling of products and deposited films adhering during etching and film-forming processes, and to perform frequent device cleaning, parts replacement, etc. Reduces productivity and increases the cost of etching and film formation, and suppresses the generation of fine particles, as well as parts for semiconductor manufacturing equipment and compound semiconductor manufacturing equipment, and particles into the substrate Suppress contamination and contamination of impurities, and cope with highly integrated semiconductor devices, etc., and improve operating rate And its object is to provide a semiconductor manufacturing apparatus and producing a compound semiconductor device that allows to achieve such greater reduction of etching and deposition costs.

  According to the nitride sprayed coating deposited without melting the supply powder at the time of thermal spraying as in the present invention, surface defects can be reduced because molten particles are hardly generated. At the same time, it is possible to increase the density of the thermal spray coating and smooth the surface, thereby reducing internal defects. Furthermore, since the stability of the crystal structure of the nitride constituting the thermal spray coating is increased, the chemical stability of the thermal spray coating can be improved.

  By applying such a nitride spray coating to parts for semiconductor manufacturing equipment and compound semiconductor manufacturing equipment using plasma discharge, the plasma resistance of the parts can be improved, and the amount of particles generated and impurity contamination The amount can be reduced, and the number of device cleaning and parts replacement can be greatly reduced. Reduction of the amount of generated particles greatly contributes to the improvement of the yield of various thin films processed by the semiconductor manufacturing apparatus and the compound semiconductor manufacturing apparatus, as well as elements and parts using the thin films. In addition, 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.

  A component for a semiconductor manufacturing apparatus and a component for a compound semiconductor manufacturing apparatus according to the present invention include a component main body and a thermal spray coating integrally formed on the surface of the component main body by spraying nitride particles. In addition, the thermal spray coating is formed by depositing 90% by mass or more of nitride powder particles in an unmelted state.

  A semiconductor manufacturing apparatus and a compound semiconductor manufacturing apparatus according to the present invention include a semiconductor manufacturing apparatus component and a compound semiconductor manufacturing apparatus component each including the sprayed coating.

  According to the present invention, generation of fine particles generated from a component is stably and effectively suppressed, and it is possible to suppress a decrease in productivity and an increase in component cost due to frequent device cleaning and component replacement. It can also be applied to the manufacture of highly integrated semiconductor devices, and it can be used for semiconductor manufacturing equipment parts and compound semiconductor manufacturing equipment parts that can reduce the cost of etching and film formation by improving the operating rate. A semiconductor manufacturing apparatus or a compound semiconductor manufacturing apparatus can be provided.

It is a schematic diagram for demonstrating the principle of a thermal spraying method. It is a schematic diagram of a flat shape sprayed particle. Is an electron micrograph showing the surface morphology of the aluminum oxide film formed by Ar + H ₂ plasma spraying. It is the electron micrograph which expanded the principal part of FIG. It is an electron micrograph which shows the surface form of the aluminum oxide film formed by Ar + and He plasma spraying. It is the electron micrograph which expanded the principal part of FIG. It is an electron micrograph which shows the surface form of the aluminum nitride film which is one Example of this invention. It is the electron micrograph which expanded the principal part of FIG. It is sectional drawing which shows the structure of the microwave etching apparatus which shows an example of the dry etching apparatus as a semiconductor manufacturing apparatus concerning this invention.

  DESCRIPTION OF SYMBOLS 1 ... Supply powder, 2 ... Heat source, 3 ... Heating medium, 4 ... Molten particle, 5 ... Acceleration gas, 6 ... Spraying torch, 7 ... Base material, 8a ... Flat particle, 9 ... Crevice, 10 ... Processing chamber, 11 ... Discharge tube, 12 ... Gas supply port, 13 ... Exhaust port, 14 ... Sample stage, 15 ... High frequency power supply, 16 ... Waveguide, 17 ... Solenoid coil, 18 ... Magnetron, 19 ... Wafer, 20 ... Thermal spray coating.

  Hereinafter, modes for carrying out the present invention will be described.

For the purpose of reducing the number of exchange of particles and parts in the plasma etching apparatus, it is effective to form a nitride film having plasma resistance and corrosion resistance on the parts irradiated with active radicals by plasma. Examples of the nitride having plasma resistance and corrosion resistance include aluminum nitride (AlN), boron nitride (BN), silicon nitride (Si ₃ N ₄ ), and the like. Examples of the composite nitride include Al—B—N. The present invention exhibits a predetermined effect because it has a coating structure in which nitride powder particles are unmelted and deposited by 90 mass% or more.

  In general, as shown in FIG. 1, a coating 8 formed by a thermal spraying method melts a raw material such as powder (feed powder 1) using electricity or combustion gas as a heat source 2, and melts the molten particles 4 into Ar gas or compressed air. It is formed by a method of spraying and spraying from the spraying torch 6 using an acceleration gas 5 such as. Therefore, when the molten particles 4 are deposited on the coating (base material 7), as shown in FIG. 1, the molten particles 4 are flattened by collision energy to become flat particles 8a, and this flat particle 8a is deposited. (Lamellar structure) is obtained. As shown in FIG. 2, the flat particles 8a described here have a ratio (X / Y) of 2.5 (X) to (Y) in the film thickness direction of the thermal spray coating 8 of 2.5 or more. Defined as particle.

  However, in the case of the coating structure in which the flat particles 8a are deposited, as shown in FIGS. 3 to 6, since the particles colliding when the molten particles 4 are deposited are scattered and adhered as the scattered particles 21, they are scattered on the flat particles 8a. The surface morphology is such that the particles 21 are deposited in an unstable manner. When a part on which the thermal spray coating 8 having such a surface form is formed is used as it is in a semiconductor manufacturing apparatus or a compound semiconductor manufacturing apparatus, an adhesion film is deposited on the part according to the form of thermal spraying. The form is easy to occur. Further, when the molten particles 4 are deposited, the flattened molten particles are rapidly cooled and solidified, so that the microcracks 22 are generated in the flat particles 8a as shown in FIGS. The crater 23 is generated.

  In particular, when oxide ceramics is used as a thermal spray material, the occurrence of cracks becomes significant. Therefore, when such a sprayed coating is used in a semiconductor manufacturing apparatus and a compound semiconductor manufacturing apparatus, the cracks 21 of the flat particles 8a develop due to the thermal stress caused by the plasma, and the strength of the sprayed coating 8 decreases, and the adhered film is formed. The problem that the crack 21 propagates and causes film peeling occurs. Furthermore, since the sprayed coating is formed in a molten state, when the composite oxide is used as the raw material powder, the composite oxide is separated and deposited due to the difference in melting point, and the material characteristics of the composite oxide cannot be obtained. There also arises a problem that the plasma resistance and corrosion resistance are lost.

  Further, when blasting is performed using alumina abrasive grains, there is a problem that the alumina abrasive grains bite into the component parts and the residual alumina causes a decrease in the adhesion of the sprayed coating. Furthermore, since a crushed layer in which microcracks caused by blast shots are present on the surface of the parts subjected to blasting, the adhesion between the sprayed coating and the sputter deposited film is reduced.

  As a result of intensive studies, the inventors have made it possible to reduce the temperature of the frame and increase the speed of the supplied powder particles by remodeling the spray nozzle of the ultra-high speed flame spraying equipment. This is the first time that thermal spraying equipment has realized that a film is formed by continuously depositing on a substrate without melting the material. Specifically, this is realized by changing the shape of the combustion chamber, making the nozzle pores, and adding an auxiliary combustion mechanism. Since it has become possible to deposit particles in an unmelted state, it has been impossible to form a film with a nitride that has been melted and sublimated by the thermal spraying method so far, but the nitride particles are in an unmelted state. Therefore, a nitride film can be formed.

  As shown in FIG. 7 and FIG. 8, the aluminum nitride film obtained by this equipment forms a film in a form in which fine particles 24 are bonded, and has a film structure in which unmelted particles are deposited. It exhibits a surface morphology free from surface defects such as cracks, craters and scattered particles as found in the sprayed film.

  According to such a nitride spray coating deposited without melting the supply powder during thermal spraying, it is used in semiconductor manufacturing equipment and compound semiconductor manufacturing equipment such as plasma etching equipment, plasma CVD equipment and sputtering equipment using plasma discharge. It was found that the plasma resistance of the parts can be significantly improved, the particle can be reduced, the impurity contamination can be reduced, and the life of the parts can be extended.

  The component for semiconductor manufacturing apparatus and the component for compound semiconductor manufacturing apparatus in the present invention have a sprayed coating of nitride particles on the surface of the component main body, and the nitride powder particles are unmelted and deposited by 90 mass% or more for thermal spraying. It is characterized by forming a film. The nitride particles preferably maintain the crystal structure of the raw material powder. For this reason, the thermal spray coating of the present invention has high chemical stability, and even when composite nitride particles are used, the material characteristics of the raw material powder can be obtained without separation due to the difference in melting point.

  Further, since the sprayed coating has a fine particle deposition structure, the gaps 9 between the deposited particles shown in FIG. 1 are small, and the sprayed coating 8 can be formed at a high density. It is possible to prevent intrusion of radicals (for example, active F radicals and Cl radicals) by attack, and it is possible to reduce impurity contamination from components.

  In addition, since the surface of the coating is a bonded form of fine particles, the adhesion film deposited on it is also an adhesion film form that stably deposits, and it is possible to stably and effectively suppress peeling of the deposits deposited on the part. it can. Further, since there is no generation of protrusions that induce the generation of particles formed on the melt-deposited sprayed coating, an effect of greatly reducing the amount of generated particles can be obtained.

  As a result, it is possible to reduce wear due to plasma attack and radical attack and the amount of particles generated due to wear, and to improve the plasma resistance and corrosion resistance of the nitride sprayed coating. Furthermore, the generation of cracks in the fine particles and the adhesion of scattered particles can be suppressed.

Further, nitride particles to be formed a sprayed coating is aluminum nitride (AlN) particles, it is preferably contained in addition to aluminum oxide (Al 2 _{O 3)} is less than 10 wt% of a nitride of unmelted. Aluminum nitride coating has higher corrosion resistance against active radicals from fluorine plasma and chlorine plasma than yttrium oxide coating, and the amount of corrosion products generated in the coating itself is extremely small, reducing the frequency of parts replacement due to wear. Is obtained. In addition, since aluminum nitride has high plasma etching property, an aluminum nitride sprayed coating on which unmelted particles are deposited has a particularly high effect.

  The sprayed coating of aluminum nitride collides particles at a high speed and forms a coating with the collision energy, but when the aluminum nitride particles are coated by thermal spraying, the surface of the aluminum nitride particles changes to aluminum oxide. . The aluminum oxide film formed on the surface of the aluminum nitride particles serves to facilitate the formation of the film by promoting bonding between the particles. For this reason, the sprayed coating of aluminum nitride has a coating structure containing aluminum oxide, but the ratio of aluminum oxide contained in the coating of aluminum nitride is preferably 10% or less.

This is due to the reason explained below. When the content ratio of aluminum oxide exceeds 10% by mass, the bonding force between particles is improved, but wear due to plasma etching is likely to occur, and the amount of generated particles may increase. Moreover, when the content ratio of aluminum oxide is 10% by mass or less, wear due to plasma attack and radical attack is reduced, the amount of particles generated is reduced, and plasma resistance is improved. A more preferable value of the content ratio is 5% by mass or less, and more preferably 3% by mass or less. In addition, in order to acquire the containing effect of aluminum oxide, 2 mass% or more is preferable. However, when the content of aluminum oxide is 0.2% or more, the particle bond of aluminum nitride is improved, so the lower limit is preferably 0.2% or more. The effect of adding aluminum oxide can be obtained not only when the thermal spray material is AlN but also when Si ₃ N ₄ or BN is used.

  The porosity of the thermal spray coating is desirably 5% or less. Thereby, the plasma inflow into the pores can be suppressed and the bond strength between the particles constituting the thermal spray coating can be increased, so that the generation of particles due to wear can be reduced. If this porosity exceeds 5%, plasma etching occurs intensively in the pores, which may promote the generation of particles from that portion, and the thermal spray coating may be easily peeled off, resulting in the number of parts replacement. May increase and decrease productivity. A more preferable range of the porosity is 1% or less.

  The surface roughness of the thermal spray coating is desirably 5 μm or less in terms of the average roughness Ra. Thereby, since the part where plasma etching concentrates can be reduced, wear due to acceleration of etching can be reduced, and the life of the sprayed coating can be extended. On the other hand, when the average roughness Ra exceeds 5 μm, plasma concentration occurs on the convex portion and the portion is selectively etched, which may increase the number of particles and reduce the service life. A more preferable range of the average roughness Ra is 3 μm or less.

  In addition, in an etching apparatus using high-density plasma, it is sometimes necessary to insulate parts. In this case, after depositing a highly insulating aluminum oxide film, a two-layer structure in which an aluminum nitride film is formed thereon The coating becomes effective. For insulation, it is important to adjust the thickness of the aluminum oxide film and to form a high-density film. Especially when an aluminum oxide film having an α structure is densely formed, a further effect is exhibited. It is preferable to set the conditions equivalent to the formation.

  Although the lower layer is an aluminum oxide film, other oxides, nitrides, or a mixture thereof may be used, and it is preferable to select a material according to necessary characteristics. Further, the effect is exhibited even when an aluminum nitride film is formed and then the outermost surface of the film is fluorinated to form a fluoride film.

  The thickness of the thermal spray coating according to the present invention is preferably 10 μm or more, more preferably 50 μm or more. The upper limit of the thermal spray coating is not particularly limited, but it is preferably 500 μm or less because no further effect can be obtained even if it is excessively thick.

  By controlling to such a coating structure, plasma resistance and corrosion resistance are greatly improved, so it becomes possible to reduce impurity contamination from the parts, and to remove the deposits deposited on the parts stably and effectively. Can be suppressed. In addition, since the surface of the coating is a bonded form of fine particles, the deposited film deposited on the surface also forms an adhered film that stably deposits, and projections that induce the generation of particles formed on the melt deposited thermal sprayed coating. Since there is no generation, an effect of greatly reducing the generation amount of particles can be obtained.

  In addition, since powder is sprayed at high speed and particles are deposited with the impact energy, blasting is not required when depositing coatings on components, and there is no blasting material residue or surface defects. The adhesion of the coating is improved. This is because the surface oxide film of the component is destroyed by high-speed collision of particles, and the active surface is exposed, so that a film is formed directly on the surface of the part. It is thought that it occurs and is formed as a film.

  Therefore, it is possible to suppress the generation of particles due to the peeling of the deposits deposited on the device parts, and it is possible to greatly reduce the number of times of device cleaning and component replacement. 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 a compound semiconductor manufacturing apparatus, as well as elements and components using the thin films. In addition, 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.

  As described above, it is effective to deposit a nitride spray coating densely in an unmelted state to reduce the number of particles in the plasma etching apparatus and reduce the number of parts replacement (long life). By using the selected sprayed powder, the porosity is small and the optimum sprayed surface roughness can be obtained, so that it is possible to achieve a surface form and sprayed structure with high plasma etching resistance, and the effects of both are demonstrated synergistically. A sprayed coating is obtained.

  In order to increase the density or the denseness of the coating, it is important to deposit the fine powder without melting it, and it is necessary to accelerate it beyond the critical speed at which the fine powder starts to deposit. For this purpose, the fine powder particles are preferably several μm or less. However, if the particles are excessively small, the particles form aggregates and the aggregates are bonded to each other, so that densification is inhibited and adhesion of the deposited particles is reduced. In particular, when the deposited film is formed thick, the shape of the fine powder is preferably an angular shape like a pulverized powder rather than a spherical shape.

  After adjusting the surface roughness of the coating with fine powder in this way, if the coating surface is further sprayed with dry ice pellets to perform cleaning treatment to remove particles that are likely to fall off, fine particles can be removed. Since the surface roughness is reduced, dry eye screening is preferably performed. Further, after the coating is formed, post-processing may be performed by polishing and mirror finishing. However, since the minute foreign matter by the surface processing remains on the surface and easily becomes a generation source of particles, it is preferable to perform a removal cleaning process by spraying dry ice pellets after the processing.

  As a specific method for obtaining a thermal spray coating of nitride particles, it is desirable to use the thermal spraying conditions appropriately selected according to the constituent material and shape of the component body, the environmental conditions used, the thermal spray material, etc. . Specifically, in order to control the size of the unfused bonded particles, fine nitride particles having a powder particle size of about several microns are used. Further, in order to control the size of the binding particles and the surface roughness of the sprayed coating, a desired binding particle size and surface roughness can be obtained by selecting and using a particle size range of the supplied powder. The average particle size of the supplied powder is preferably 10 μm or less, and more preferably 1 μm or more and 3 μm or less. Then, by controlling the spraying conditions such as the gas flow rate, pressure, spraying distance, nozzle diameter, and material supply amount, the sprayed coating structure in which unmelted particles are bonded, the surface roughness, the porosity, and the like can be controlled.

  The critical speed at which the fine powder starts to deposit due to the impact energy varies depending on the material of the fine powder to be used, but the fine powder deposition is started by setting the speed of the fine powder particles to about 400 m / sec to 800 m / sec. As a result, a film is formed. In order to obtain this particle velocity, particles are deposited without blasting by spraying the fine powder with the combustion gas, so it is necessary to select a gas type. It is preferable to use combustion energy such as acetylene, oxygen, and kerosene as the combustion gas.

  Next, an embodiment of the semiconductor manufacturing apparatus of the present invention will be described. FIG. 9 is a schematic diagram showing a main configuration of a plasma etching apparatus which is an embodiment of the semiconductor manufacturing apparatus of the present invention.

  Plasma etching processing of various thin films such as insulating films, electrode films, and wiring films formed on a substrate or microfabrication of Si is performed by utilizing the interaction between a microwave electric field and a magnetic field as shown in FIG. It can be carried out using a microwave etching apparatus that converts gas into plasma.

  A quartz discharge tube 11 is provided in the upper portion of the vacuum apparatus processing chamber 10, a gas supply port 12 for introducing an etching gas is disposed in the processing chamber 10, and a vacuum exhaust port 13 is provided. The processing chamber 10 is provided with a sample stage 14 on which a wafer is placed. A high frequency power supply 15 is connected to the sample stage 14 so that high frequency power is applied to the sample stage 14. A waveguide 16 is provided outside the discharge tube 11, and a solenoid coil 17 for generating a magnetic field in the discharge tube is further provided outside the waveguide 16. A magnetron 18 that oscillates microwaves is provided at the end of the waveguide 16.

  In this etching apparatus, an etching gas is introduced from the gas supply port 12 into the processing chamber 10, and the processing chamber 10 is evacuated, and then the microwave from the magnetron 18 is introduced into the discharge tube 11 through the waveguide 16, and the solenoid coil. A magnetic field is formed by 17, and the etching gas in the discharge tube 11 is turned into plasma by the interaction between the microwave electric field and the magnetic field by the solenoid coil 17. Further, high frequency power is applied to the sample stage 14 from the high frequency power source 15 to generate a bias voltage, and ions in the plasma are drawn to the wafer 19 side to perform anisotropic etching. The thermal spray coating 20 containing unmelted nitride particles is formed on the inner surface of a quartz discharge tube 11 as a component body.

  Since the thermal spray coating 20 can reduce wear due to plasma and radicals as described above, generation of particles due to peeling of the thermal spray coating 20 can be reduced. At the same time, since the quartz surface of the discharge tube 11 can be prevented from being exposed, generation of particles due to peeling from the quartz surface can be reduced.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the following examples.

Example 1
An AlN film having a film thickness of 50 μm was formed on the inner surface of the discharge tube 11 made of quartz, which is a component of the plasma etching apparatus as shown in FIG. That is, using an ultra-high-speed flame spraying equipment, an oxygen flow rate of 138 cc / min, a kerosene supply rate of 133 cc / min, a supply acetylene pressure of 30 psi were set, and an AlN powder material having an average particle size of 2.3 μm was injected together with combustion gas, An AlN film was formed by depositing on the surface of each part. At that time, the spraying distance was set in the range of 130 to 160 mm as shown in Table 1. Next, by cleaning the surface of the AlN coating by spraying dry ice pellets onto the surface of the AlN coating at a pressure of 5 kg / cm ² , each part on which the AlN coating was formed is then subjected to conditions of a temperature of 200 ° C. × 2 hours. And dried.

In the plasma etching apparatus thus prepared, plasma etching of an aluminum alloy film on an 8-inch wafer is performed using a mixed gas of BCl ₃ + Cl ₂ + N ₂ , and the average particle generation amount up to a predetermined number of wafers processed A comparative study with the number of wafers processed was performed.

  The amount of particles generated was determined by measuring the number of particles having a diameter of 0.2 μm or more mixed on an 8-inch wafer with a particle counter. In addition, the service life was confirmed by the number of wafers processed immediately before the amount of particles generated increased rapidly and exceeded 50. These results are shown in Table 1.

(Example 2)
A Si ₃ N ₄ coating 20 having a thickness of 50 μm was formed on the inner surface of a discharge tube 11 made of quartz, which is a component of the plasma etching apparatus as shown in FIG. That is, using an ultra-high-speed flame spraying equipment, setting an oxygen flow rate of 128 cc / min, a kerosene supply rate of 130 cc / min, and a supply acetylene pressure of 30 psi, an Si ₃ N ₄ powder material having an average particle size of 2.3 μm is injected together with combustion gas The Si ₃ N ₄ coating 20 was formed by depositing on the surface of each component. At that time, the spraying distance was set in the range of 130 to 160 mm as shown in Table 1. Then, by spraying the dry ice pellets at a pressure 5 kg / cm ² on the surface of the _Si 3 _{N 4} film 20, and a cleaning process the _Si 3 _{N 4} film 20 side, the _Si 3 _{N 4} film 20 thereafter Each formed part was dried at a temperature of 200 ° C. for 2 hours.

In the plasma etching apparatus thus prepared, plasma etching of an aluminum alloy film on an 8-inch wafer is performed using a mixed gas of BCl ₃ + Cl ₂ + N ₂ , and the average particle generation amount up to a predetermined number of wafers processed A comparative study with the number of wafers processed was performed.

  The amount of particles generated was determined by measuring the number of particles having a diameter of 0.2 μm or more mixed on an 8-inch wafer with a particle counter. In addition, the service life was confirmed by the number of wafers processed immediately before the amount of particles generated increased rapidly and exceeded 50. These results are shown in Table 1.

(Example 3)
A BN coating 20 having a film thickness of 50 μm was formed on the inner surface of a quartz discharge tube 11 as a component of the plasma etching apparatus as shown in FIG. That is, using an ultra-high-speed flame spraying equipment, setting an oxygen flow rate of 130 cc / min, a kerosene supply amount of 135 cc / min, and a supply acetylene pressure of 30 psi, BN powder material having an average particle size of 2.2 μm is injected together with combustion gas, A BN coating 20 was formed by depositing on the surface of each component. At that time, the spraying distance was set in the range of 140 to 160 mm as shown in Table 1. Next, the BN coating surface is cleaned by spraying dry ice pellets onto the surface of the BN coating 20 at a pressure of 5 kg / cm ² , and then each part on which the BN coating 20 is formed is heated to 200 ° C. for 2 hours. The drying process was performed on the conditions of these.

In the plasma etching apparatus thus prepared, plasma etching of an aluminum alloy film on an 8-inch wafer is performed using a mixed gas of BCl ₃ + Cl ₂ + N ₂ , and the average particle generation amount up to a predetermined number of wafers processed A comparative study with the number of wafers processed was performed.

  The amount of particles generated was determined by measuring the number of particles having a diameter of 0.2 μm or more mixed on an 8-inch wafer with a particle counter. In addition, the service life was confirmed by the number of wafers processed immediately before the amount of particles generated increased rapidly and exceeded 50. These results are shown in Table 1.

Example 4
After the Al ₂ O ₃ coating 20 having a film thickness of 60 μm is formed on the inner surface of the discharge tube 11 made of quartz, which is a component of the plasma etching apparatus as shown in FIG. 9, the Al ₂ O ₃ An AlN film of 50 μm was formed on the film 20. That is, using an ultra-high-speed flame spraying equipment, oxygen flow rate of 132 cc / min, kerosene supply rate of 138 cc / min, supply acetylene pressure of 30 psi, and Al ₂ O ₃ powder material with an average particle size of 2.1 μm are injected together with combustion gas The Al ₂ O ₃ coating 20 was formed by depositing on the surface of each component. At that time, the spraying distance was set to 130 to 160 mm. Next, using an ultra-high-speed flame spraying equipment, an oxygen flow rate of 138 cc / min, a kerosene supply rate of 133 cc / min, and a supply acetylene pressure of 30 psi were set, and an AlN powder material having an average particle size of 2.3 μm was injected together with the combustion gas. An AlN coating was formed by depositing on the surface of the Al ₂ O ₃ coating. By spraying dry ice pellets onto the surface of the AlN film at a pressure of 5 kg / cm ² , the surface of the AlN film is cleaned, and then each part on which the AlN film is formed is dried at a temperature of 200 ° C. for 2 hours. Was given.

In the plasma etching apparatus thus prepared, plasma etching of an aluminum alloy film on an 8-inch wafer is performed using a mixed gas of BCl ₃ + Cl ₂ + N ₂ , and the average particle generation amount up to a predetermined number of wafers processed A comparative study with the number of wafers processed was performed.

  The amount of particles generated was determined by measuring the number of particles having a diameter of 0.2 μm or more mixed on an 8-inch wafer with a particle counter. In addition, the service life was confirmed by the number of wafers processed immediately before the amount of particles generated increased rapidly and exceeded 50. These results are shown in Table 1.

(Comparative Example 1)
An Al ₂ O ₃ sprayed coating having a thickness of 50 μm was formed on the inner surface of the discharge tube 11 made of quartz, which is a component of the plasma etching apparatus as shown in FIG. That is, by using the plasma spraying equipment, current 650A, voltage 55V, Ar gas flow rate / pressure set to 75/80, the _Al 2 _{O 3} powder material having an average particle diameter of 32μm and allowed deposited each part surface Al ₂ An O ₃ sprayed coating was formed. At that time, the spraying distance was set in the range of 120 to 150 mm as shown in Table 1. Thereafter, each part on which the Al ₂ O ₃ sprayed coating was formed was subjected to a drying treatment under the condition of a temperature of 200 ° C. × 2 hours.

In the plasma etching apparatus thus prepared, plasma etching is performed on an aluminum alloy film formed on an 8-inch wafer using a mixed gas of BCl ₃ + Cl ₂ + N ₂ , and the average particle size up to a predetermined number of wafers processed A comparison between the generation amount and the number of wafers processed until just before the generation amount of particles exceeds 50 is shown in Table 1 below.

(Comparative Example 2)
An AlN film having a film thickness of 50 μm was formed on the inner surface of the discharge tube 11 made of quartz, which is a component of the plasma etching apparatus as shown in FIG. At that time, AlN raw material powder containing 40% (sample 15), 30% (sample 16) and 20% (sample 17) of Al ₂ O ₃ was used. As in Example 1, the treated product uses an ultra-high-speed flame spraying equipment, and is set to an oxygen flow rate of 138 cc / min, a kerosene supply rate of 133 cc / min, a supply acetylene pressure of 30 psi, and an AlN powder material having an average particle size of 1.8 μm. Was sprayed together with the combustion gas and deposited on the surface of each of the above components to form an AlN coating. At that time, the spraying distance was set in the range of 130 to 160 mm as shown in Table 1. Next, by cleaning the surface of the AlN coating by spraying dry ice pellets onto the surface of the AlN coating at a pressure of 5 kg / cm ² , each part on which the AlN coating was formed is then subjected to conditions of a temperature of 200 ° C. × 2 hours. And dried.

In the plasma etching apparatus thus prepared, plasma etching is performed on an aluminum alloy film formed on an 8-inch wafer using a mixed gas of BCl ₃ + Cl ₂ + N ₂ , and the average particle size up to a predetermined number of wafers processed A comparison between the generation amount and the number of wafers processed until just before the generation amount of particles exceeds 50 is shown in Table 1 below.

(Example 5)
An AlN coating 20 having a thickness of 50 μm was formed on the inner surface of a quartz discharge tube 11 as a component of the plasma etching apparatus as shown in FIG. That is, using an ultra-high-speed flame spraying equipment, an oxygen flow rate of 138 cc / min, a kerosene supply rate of 133 cc / min, a supply acetylene pressure of 30 psi, an AlN powder material having an average particle size of 1.6 μm is injected together with combustion gas, An AlN film 20 was formed by depositing on the surface of each part. At that time, the spraying distance was set in the range of 130 to 160 mm as shown in Table 1. Next, by spraying dry ice pellets onto the surface of the AlN coating at a pressure of 5 kg / cm ² , the cleaning process of the AlN coating surface was performed, and then each part on which the AlN coating 20 was formed was heated at a temperature of 200 ° C. × 2 hours. A drying treatment was performed under the conditions.

In the plasma etching apparatus thus prepared, plasma etching of the SiO ₂ film formed on the 8-inch wafer is performed using a mixed gas of CF ₄ + O ₂ + Ar, and the average generation of particles up to a predetermined number of wafers processed The amount and the number of processed wafers were compared and the results are shown in Table 1 below.

(Comparative Example 3)
A Y ₂ O ₃ film having a thickness of 50 μm was formed on the inner surface of the discharge tube 11 made of quartz, which is a component of the plasma etching apparatus as shown in FIG. That is, a thermal spray coating made of an oxide of Y ₂ O ₃ using a Y ₂ O ₃ powder having an average particle size of 33 μm, by setting the current 550 A, voltage 75 V, Ar gas flow rate / pressure to 100/100 by plasma spraying. Formed. At that time, the spraying distance was set in the range of 130 to 150 mm as shown in Table 1. On the surface of each particle constituting the sprayed coating, an Al oxide film of impurities contained in the raw material powder was formed.

In the plasma etching apparatus thus prepared, plasma etching of the SiO ₂ film on the 8-inch wafer is performed using a mixed gas of CF ₄ + O ₂ + Ar, and the average particle generation amount up to a predetermined number of wafers processed and the wafer Comparison with the number of processed sheets was performed, and the results are shown in Table 1 below.

  The surface roughness Ra and the porosity of the thermal sprayed coatings of Examples 1 to 5 and Comparative Examples 1 to 3 were confirmed by the method described below, and the results were as follows. This is also shown in Table 1.

(Surface roughness Ra of thermal spray coating)
The arithmetic average roughness defined by the Japanese Industrial Standard (JIS B 0601-1994) was defined as the surface roughness Ra.

(Porosity of sprayed coating)
The cross-sectional structure cut in the film thickness direction of the thermal spray coating was observed with an optical microscope at a magnification of 500 times, and the area of the pores was measured in an observation field of 210 μm in length and 270 μm in width. From the following equation (1), the porosity (% ), And the average value at 10 locations in each field of view is shown in Table 1 below as the porosity.
Porosity (%) = (S2 / S1) × 100 (1)
However, S1 is 210 μm long × 270 μm wide viewing area (μm ² ), and S2 is the total area (μm ² ) of holes in the 210 μm × 270 μm viewing field.

(Crystal structure ratio of particles constituting the thermal spray coating)
The surface of the sprayed coating was analyzed by X-ray mass spectrometry, and the content of Al ₂ O ₃ was calculated from the peak intensity ratio of the main peak of AlN and the main peak of Al ₂ O ₃ . Further, when Si ₃ N ₄ or BN is used as the thermal spray material, the content of each oxide is determined from the peak intensity ratio between the main peak of the thermal spray material and the main peak of each oxide (SiO ₂ or B ₂ O ₃ ). The amount was calculated.

  As is apparent from the results shown in Table 1, in the case of the plasma etching apparatus according to Examples 1 to 5, it has been found that the amount of generated particles is smaller and the service life is longer than those of Comparative Examples 1 to 3. From these, it was confirmed that the generation of particles can be effectively and stably prevented by the thermal spray coatings of Examples 1 to 5 and the service life can be extended.

In each of the above embodiments, the thermal spray coating is directly formed on the surface of the component main body. However, at least one oxide film made of Al ₂ O ₃ or the like is formed on the surface of the component main body, and the outermost surface thereof. By forming a sprayed coating on the surface, the effect of enhancing the insulation as a part is exhibited.

  As described above, according to the component for a semiconductor manufacturing apparatus and the component for a compound semiconductor manufacturing apparatus according to the present invention, particles generated from the component parts can be stably and effectively prevented, and the coating film for preventing peeling itself. It becomes possible to improve the stability of the. Therefore, it is possible to reduce the number of times of cleaning and part replacement of the semiconductor manufacturing apparatus and the compound semiconductor manufacturing apparatus. Further, according to the semiconductor manufacturing apparatus and the compound semiconductor manufacturing apparatus of the present invention having such a component for a semiconductor manufacturing apparatus and a component for a compound semiconductor manufacturing apparatus, particles in a film that causes a defect in a wiring film or an element are generated. Mixing can be suppressed, and productivity can be improved and the cost of consumable parts can be reduced.

  Note that the present invention is not limited to the above-described embodiment as it is, and can be embodied by modifying the constituent elements without departing from the scope of the invention in the implementation stage. In addition, various inventions can be formed by appropriately combining a plurality of components disclosed in the embodiment. For example, some components may be deleted from all the components shown in the embodiment. Furthermore, constituent elements over different embodiments may be appropriately combined.

  In the present embodiment, the method of generating the plasma of the processing gas has been described using the interaction between the microwave electric field and the magnetic field, but the method of generating the plasma is not limited to this, for example, The same effects can be applied to plasma generators such as those using parallel plate electrodes, those using high frequency coils, and those using inductive energy.

Claims (8)

  A component for a semiconductor manufacturing apparatus comprising a component main body and a thermal spray coating formed on the surface of the component main body by thermal spraying of nitride particles as a raw material powder, wherein the thermal spray coating is an unmelted nitride powder particle A component for semiconductor manufacturing equipment, characterized in that it is deposited by 90% or more.   2. The semiconductor manufacturing apparatus component according to claim 1, wherein a balance other than the nitride of the thermal spray coating is an oxide, and the unmelted nitride particles maintain a crystal structure of a raw material powder. Parts for semiconductor manufacturing equipment.   3. The semiconductor manufacturing apparatus component according to claim 1, wherein the nitride particles are at least one of aluminum nitride, boron nitride, and silicon nitride. 4. The semiconductor manufacturing apparatus component according to claim 1, wherein the nitride particles are aluminum nitride (AlN) particles, and the spray coating is an oxide other than unmelted nitride. 5. A component for a semiconductor manufacturing apparatus, containing 10% by mass or less of aluminum oxide (Al ₂ O ₃ ) as   5. The semiconductor manufacturing apparatus component according to claim 1, wherein the thermal spray coating has a porosity of 5% or less. 6.   6. The semiconductor manufacturing device component according to claim 1, wherein the thermal spray coating has a surface roughness of 5 [mu] m or less in terms of arithmetic average roughness Ra.   7. The component for a semiconductor manufacturing apparatus according to claim 1, wherein at least one oxide film is formed on the surface of the component main body, and the sprayed film is an outermost surface of the oxide film. A component for a semiconductor manufacturing apparatus, characterized in that it is formed.   A semiconductor manufacturing apparatus comprising the component for a semiconductor manufacturing apparatus according to claim 1.

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