JP2010153424A - Electronic device manufacturing apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electronic device manufacturing apparatus in which an Al alloy member having a surface protective film excellent in corrosion resistance is used at least for one part. <P>SOLUTION: In the electronic device manufacturing apparatus using an Al alloy member 74 at least for one part, at least one part of the surface of the Al alloy member 74 is covered with a nonporous anodized film 73 containing an non-aqueous solvent, the anodized film 73 is covered with a fluorocarbon film or polymer fluorocarbon film 72, and the one part of the surface of the Al alloy member is a portion to contact a corrosive solution. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an electronic device manufacturing apparatus using an Al (aluminum) alloy member that is lightweight and excellent in mechanical strength.

  Semiconductor devices, flat display panels, and other various electronic device manufacturing equipment are usually made of stainless steel, but for example, large substrates (2.88m x 3.08m) are processed to produce large displays. Therefore, the use of a lightweight metal such as an Al alloy has been studied. However, in the manufacturing apparatus for large substrates as described above, the Al alloy is deformed by its own weight, and an O-ring or the like for maintaining airtightness does not work. Therefore, an Al alloy having excellent strength is demanded.

  On the other hand, since the inner surface of various electronic device manufacturing devices is exposed to corrosive chemicals, corrosive gases, plasma, etc., the inner surface is covered with a strong passive protective film even if it is made of Al alloy. Need to be. Accordingly, there is a particular need for an Al alloy that can be covered with a passive protective film having excellent strength and a strong surface.

  As an Al alloy capable of increasing the mechanical strength and covering the surface with a strong passivation protective film, for example, the one shown in Patent Document 1 (Japanese Patent Laid-Open No. 9-176762) is known. However, the material disclosed in Patent Document 1 is insufficient in strength to be applied to a recent large-scale manufacturing apparatus, and the fluorinated passive film disclosed in Patent Document 1 is permeable to gas. It is insufficient for various corrosive gases and plasmas.

  The present inventors have proposed that an Al alloy to which Mg and Zr are added is used to obtain a passivation protective film by anodizing the surface with a non-aqueous solution (Patent Document 2: International Publication No. WO2006 / 134737). However, the material disclosed in Patent Document 2 is insufficient in strength to be applied to recent large-scale manufacturing apparatuses, and the anodized film disclosed in Patent Document 2 is made of hydrofluoric acid or the like. Etching into a corrosive liquid results in insufficient corrosion resistance.

  Patent Document 3 (Japanese Patent Application Laid-Open No. 1-272739) describes a color forming aluminum alloy containing a color forming element. However, Patent Document 3 (Japanese Patent Application Laid-Open No. 1-272739) does not disclose a high-purity Al alloy having an extremely small unavoidable impurity content that contains only an element that increases the hardness of an aluminum alloy. There is also no disclosure of obtaining a high hardness member having a Vickers hardness of greater than 30 with a pure Al alloy. Sample No. 1 in Table 1 disclosed as an example in Patent Document 3 (Japanese Patent Laid-Open No. 1-272739). The aluminum alloy No. 8 contains not only Ce, Mg and Zr but also 4.90 wt% Zn as a color forming element.

Japanese Patent Laid-Open No. 9-176772 International Publication No. WO2006 / 134737 Pamphlet Japanese Patent Laid-Open No. 1-272739 JP 2005-29893 A JP 2004-149927 A International Publication No. WO2006 / 137384 Pamphlet JP 2007-88398 A JP 2007-287876 A

  Accordingly, an object of the present invention is to provide an electronic device manufacturing apparatus using at least a part of an Al alloy member having a surface protective film excellent in corrosion resistance.

  The electronic device manufacturing apparatus according to the present invention is as follows.

  (1) In an electronic device manufacturing apparatus using an Al alloy member as at least a part of a container, at least a part of the surface of the Al alloy member is covered with a nonporous anodic oxide film made of a nonaqueous solvent, and the anode The electronic device manufacturing apparatus according to claim 1, wherein the oxide film is covered with a fluorocarbon film or a polymerized fluorocarbon film, and the at least part of the surface of the Al alloy member is a part that comes into contact with a corrosive liquid.

  (2) In an electronic device manufacturing apparatus using an Al alloy member as at least a part of a container, the Al alloy member contains Mg, Zr and Ce in mass%, and Mg concentration exceeds 0.01% and is 5.0. %, The Ce concentration is more than 0.01% to 15.0% or less, the Zr concentration is more than 0.01% to 0.15% or less, and the balance consists of Al and inevitable impurities, and the elements of the inevitable impurities Are each 0.01% or less, and at least a part of the surface of the Al alloy member is covered with a nonporous anodic oxide film made of a nonaqueous solvent, and the anodic oxide film is covered with a fluorocarbon film or a polymerized fluorocarbon film. An electronic device manufacturing apparatus characterized by that.

  (3) The Al alloy member contains Mg, Zr and Ce in mass%, Mg concentration is over 0.01% and 5.0% or less, Ce concentration is over 0.01% and 15.0% or less, (2), wherein the Zr concentration is over 0.01% and 0.15% or less, the balance is made of Al and inevitable impurities, and the elements of the inevitable impurities are each 0.01% or less. The electronic device manufacturing apparatus described in 1.

  (4) The electronic device manufacturing apparatus according to (2) or (3), wherein the at least part of the surface of the Al alloy member is a portion that comes into contact with a corrosive liquid.

  (5) The electronic device manufacturing apparatus according to any one of (2) to (4), wherein the thickness of the anodized film is 0.01 μm to 0.6 μm.

(6) The electronic device manufacturing apparatus according to any one of (1) to (5), wherein the anodic oxide film is an amorphous Al ₂ O ₃ film.

  (7) The electronic device manufacturing apparatus according to any one of the above (1) to (6), wherein the fluorocarbon film or the polymerized fluorocarbon film has a thickness of 0.01 μm to 10 μm.

  (8) The container is a wet process container, and the container is configured to be sealed so that the internal space shuts off the atmosphere during the process. The electronic device manufacturing apparatus according to one of the above.

(9) It further includes a resin pipe for supplying chemical solution or pure water to the container, and the resin pipe has an oxygen permeability coefficient of 5 × 10 ⁶ [piece · cm / (cm ² secPa)] or less. The electronic device manufacturing apparatus according to any one of (1) to (8) above.

(10) The apparatus for manufacturing an electronic device according to (9), wherein the oxygen permeability coefficient of the resin pipe is 2 × 10 ⁶ [pieces / cm / (cm ² secPa)] or less.

  (11) The resin pipe has an inner surface formed of any one of ETFE, PTFE, PVDC, FEP, and PFA, and an outer surface formed of any of ETFE, PTFE, PVDC, FEP, and PFA. The apparatus for manufacturing an electronic device according to (9), further comprising a layer formed of nylon in the middle.

  As used herein, “anodic oxidation with a nonaqueous solvent” refers to anodization disclosed in Patent Document 2, and “anodic oxidation film with a nonaqueous solvent” in this application refers to “anodic oxidation with a nonaqueous solvent”. This is a nonporous anodic oxide film obtained by carrying out the process, which is excellent in corrosion resistance and has characteristics such as a low water release amount during use.

  ADVANTAGE OF THE INVENTION According to this invention, the electronic device manufacturing apparatus which used the Al alloy member which has the surface protection film excellent in corrosion resistance for at least one part can be obtained.

  Next, embodiments of the present invention will be described with reference to the drawings.

An Al alloy member having a surface protection film excellent in corrosion resistance, used in at least a part (container structure) of an electronic device manufacturing apparatus (for example, an air-blocking sealed cleaning apparatus) according to an embodiment of the present invention will be described. The Al alloy member having a surface protective film excellent in corrosion resistance is an Al—Mg—Ce—Zr alloy having a nonporous Al ₂ O ₃ protective film by anodization using a nonaqueous solvent.

In the following embodiments, an Al-Mg-Ce-Zr alloy having a nonporous anodic oxide film using a non-aqueous solvent will be described as an Al alloy member having a surface protective film excellent in corrosion resistance. Then, the Al alloy member having a surface protection film excellent in corrosion resistance is not limited to an Al—Mg—Ce—Zr alloy having a nonporous anodic oxide film by a nonaqueous solvent, for example, nonporous by a nonaqueous solvent. A Ce-free Al—Mg—Zr alloy having a high quality anodic oxide film (for example, an amorphous Al ₂ O ₃ film) may be used. As an Al alloy member having a surface protection film excellent in corrosion resistance, for example, the above-mentioned Ce-free Al- having a non-porous anodic oxide film (for example, an amorphous Al ₂ O ₃ film) using a non-aqueous solvent is used. Even when an Mg—Zr alloy is used, the same effect as that obtained when an Al—Mg—Ce—Zr alloy having a nonporous anodic oxide film by a nonaqueous solvent is used can be obtained.

  Referring to FIG. 1, there is shown the Vickers hardness of an Al alloy (4.5% Mg-0.1% Zr-Al) to which Ce is used as a container structure in the above air-blocking hermetic cleaning apparatus. . Four Ce additions plotted above a 4.5% Mg-0.1% Zr-Al alloy sample with 4.5% Mg addition-4.5% Mg-0.1% Zr-Al The alloy sample is a sample obtained by adding 1%, 5%, 10%, and 15% by mass of Ce to a 4.5% Mg-0.1% Zr-Al sample. These four Ce-added-4.5% Mg-0.1% Zr-Al alloy samples are more than the 4.5% Mg-0.1% Zr-Al alloy sample in which the Mg addition amount is 4.5%. It can also be seen that the Vickers hardness is improved.

  Referring to FIG. 2, the relationship between the Ce concentration (mass%) and Vickers hardness added to the 4.5% Mg-0.1% Zr-Al alloy sample, and 4.5% Mg-0.1%. The relationship between the Ce concentration (% by mass) added to the Zr—Al alloy sample and the increase rate (%) of the Vickers hardness is shown. As is apparent from FIG. 2, it can be seen that by adding Ce element to about 15.0%, the Vickers hardness exceeds 68 and is improved to about 105. Compared with 4.5% Mg-0.1% Zr-Al alloy without adding Ce, for example, 5% Ce-4.5% Mg-0.1% Zr-Al with 5% Ce added The alloy has a hardness increase of over 30%. When manufacturing the container structure of the cleaning apparatus, the container thickness can be reduced by about 30%, and the weight can be reduced.

By adding about 0.15% or less of Zr, there is an effect that grain growth is suppressed and mechanical strength is maintained even when heat treatment at about 350 ° C. is performed. Even in the annealing process in which the heat treatment after the anodizing treatment is performed in, for example, a 20% O ₂ / N ₂ atmosphere at 300 ° C. for 1 hour, it is possible to suppress a decrease in strength of the container structure.

Referring to FIG. 3, a sample obtained by anodizing a 4.5% Mg-0.1% Zr—Al alloy added with 1%, 3%, and 5% of Ce with a nonaqueous solvent was added with 100% Cl ₂ ,. The weight loss rate after sealing at 3 MPa pressure and exposure at 200 ° C. for 6 hours is shown. It was confirmed that the corrosion resistance against Cl ₂ gas was dramatically improved by adding 5% or less of Ce and anodizing with a non-aqueous solvent.

  Here, the Al alloy member added with Ce used as a container structure in the above-described air-blocking hermetic cleaning apparatus is composed of Mg, Zr and Ce in mass% and Mg concentration exceeding 0.01% and 5.0%. %, The Ce concentration is more than 0.01% to 15.0% or less, the Zr concentration is more than 0.01% to 0.15% or less, and the balance consists of Al and inevitable impurities, and the elements of the inevitable impurities May be any Al—Mg—Zr—Ce alloy with 0.01% or less.

  The Al alloy member preferably contains Mg, Zr and Ce in mass%, Mg concentration is over 0.01% and 5.0% or less, Ce concentration is over 0.01% and 5.0% or less, Zr The concentration may be more than 0.01% and 0.15% or less, the remainder may be made of Al and inevitable impurities, and the elements of the inevitable impurities may be 0.01% or less.

The above-mentioned Al-Mg-Zr-Ce alloy to which Ce is added at 15.0% or less, preferably 5.0% or less is anodized with a non-aqueous solvent, whereby the corrosion resistance against Cl ₂ gas is shown in FIG. As with the example given, it improves dramatically.

  In the present invention, the inner surface of the Al alloy member, which is a container structure, is subjected to a fluororesin coating treatment. At this time, if the fluororesin coating treatment is performed directly on the inner surface of the Al alloy member, the following problems are caused. Occurs. Fluororesin is known for its gas permeability. For example, when HCl vapor or HF vapor is generated from the cleaning chemical solution, it penetrates the fluororesin coating film and reaches the inner surface of the Al alloy member.

  Therefore, in the present invention, before the fluororesin coating treatment is applied to the inner surface of the Al alloy member, the above-described nonaqueous solvent anodic oxide film is applied to the inner surface of the Al alloy member, so that the gas permeation Al There is an effect of suppressing corrosion of the alloy surface and gas components generated by the corrosion from peeling off the fluororesin coat. Reduce metal contamination and particle contamination from the surface of the container structure.

Specifically, the anodic oxide film using a non-aqueous solvent is formed as follows. On the surface of the Ce-added Al alloy member obtained as described above, an amorphous Al ₂ O ₃ film as an anodic oxide film is formed by anodization using a non-aqueous solvent. About 0.6 μm is provided. The used non-aqueous solution contains ethylene glycol or diethylene glycol as a non-aqueous solvent and contains pure water and adipic acid as solutes. If the thickness of the anodized film is less than 0.01 μm, the effect is small, and if the thickness exceeds 0.6 μm, a remarkable effect cannot be obtained, which is economically disadvantageous.

  Next, a method for forming a fluorocarbon film as the fluororesin coating film will be described.

  First, the first fluorocarbon film forming method will be described.

In this first fluorocarbon film forming method, an organic substance is attached to the surface of a base material (an AlMgCeZr alloy having an Al ₂ O ₃ film as an anodized film by a non-aqueous solvent), and then a fluoride gas is flowed to the base material surface. A fluorocarbon film is formed.

Although this method will be described with reference to FIG. 4, the fluorocarbon film forming method used in the present invention is not limited to this method. In this method, the fluorocarbon film forming method described in Japanese Patent Application Laid-Open No. 2005-29893 (Patent Document 4) is applied to an AlMgCeZr alloy having an Al ₂ O ₃ film as an anodized film using a non-aqueous solvent. It is.

Using an apparatus shown in FIG. 4 using ethylhexyl methacrylate (hereinafter abbreviated as HEMA) as an organic monomer to be deposited and 2,2-azobisisobutyronitrile (hereinafter abbreviated as AIBN) as an initiator, a fluorocarbon film Formed. In the reaction vessel 6 which is a stainless steel pipe, an AlMgCeZr alloy 7 having an Al ₂ O ₃ film as an anodized film by a non-aqueous solvent was disposed.

Nitrogen gas is passed through the organic monomer (HEMA) 3a in the filling container 2a heated to 120 ° C. from the pipe 1a. At the same time, nitrogen gas is passed through the initiator (AIBN) 3b in the filling container 2b heated to 70 ° C. from the pipe 1b. Nitrogen gas is introduced into the reaction vessel 6 containing the gas of the organic monomer 3a, and simultaneously introduced into the reaction vessel 6 containing the gas of the initiator 3b. In this way, the organic monomer gas and the initiator gas were simultaneously adhered to the AlMgCeZr alloy 7 having the Al ₂ O ₃ film in the reaction vessel 6 at 30 ° C. for 6 hours. Thereafter, the reaction vessel 6 was sealed and heated to 90 ° C. for polymerization for 168 hours. After 168 hours had elapsed, the reaction vessel 6 was cooled to room temperature, air was introduced into the reaction vessel 6 and polymerization was stopped. Thereafter, the inside of the reaction vessel 6 was replaced with nitrogen gas, 20% F ₂ was supplied from the pipe 5 to the reaction vessel 6 at 200 ml / min, the temperature was raised to 200 ° C. at 10 ° C./min, and the reaction was allowed to proceed for 45 minutes. .

As described above, after forming a polymerized fluorocarbon film on the Al ₂ O ₃ film of the AlMgCeZr alloy 7, the AlMgCeZr alloy 7 was taken out and analyzed by an X-ray photoelectron analyzer (XPS). The results are shown in FIG.

As shown in FIG. 5, as a result of analysis, it was confirmed that a polymerized fluorocarbon film was formed because C—F ₂ and C—F ₃ bonds could be confirmed for C atoms.

  Furthermore, in order to confirm the chemical resistance of the obtained polymerized fluorocarbon coating, it was immersed in a 5 wt% hydrofluoric acid-hydrogen peroxide mixture for 24 hours. FIG. 6 shows SEM (scanning electron microscope) images before and after immersion. Since no change was observed in the SEM images before and after the immersion, it was confirmed that there was corrosion resistance against the hydrofluoric acid-hydrogen peroxide mixture.

  Next, the second fluorocarbon film forming method will be described.

In this second fluorocarbon film forming method, a carbon layer is first formed on an Al ₂ O ₃ film of a base material (AlMgCeZr alloy having an Al ₂ O ₃ film as an anodized film by a nonaqueous solvent), and a fluorocarbon is formed thereon. The layer is formed. The second fluorocarbon film formation method is the same as the fluorocarbon film formation method described in Japanese Patent Application Laid-Open No. 2004-149927 (Patent Document 5), but an AlMgCeZr alloy having an Al ₂ O ₃ film as an anodic oxide film using a non-aqueous solvent. Applied to. That is, since the carbon layer is directly formed on the Al ₂ O ₃ film of the base material and the fluorocarbon layer is formed thereon, it has sufficient corrosion resistance and can be easily formed. There are advantages. That is, there is a feature that it is not necessary to leave the nickel fluoride film on the Al ₂ O ₃ film in the process of forming the carbon layer. The thickness of the fluorocarbon layer at this time is 0.01 μm to 10 μm, preferably 0.1 μm to 0.2 μm. The carbon layer has a thickness of 0.001 μm to 1 μm, preferably 0.1 μm to 0.5 μm.

  Next, a third fluorocarbon film forming method will be described.

The third fluorocarbon film forming method, on the _Al 2 _{O 3} film of the base material (AlMgCeZr alloy having an _Al 2 _{O 3} film as an anode oxide film formed by the non-aqueous solvent), _C 5 _{F 8} a CFx film as fluorocarbon coating The gas is decomposed by argon (Ar) plasma to form CVD (Chemical Vapor Deposition).

Furthermore, after forming the CFx film or annealing the CFx film, the surface of the CFx film is nitrided by nitrogen radicals generated by introducing N ₂ gas into the Ar gas plasma, thereby reducing degassing from the CFx film. ing. This eliminates film peeling and allows the dielectric constant to be controlled in the range of 1.7 to 2.2.

This third fluorocarbon film formation method is the same as the fluorocarbon film formation method described in International Publication No. WO2006 / 137384 (Patent Document 6), except that the AlMgCeZr has an Al ₂ O ₃ film as an anodic oxide film using a non-aqueous solvent. Applied to alloys.

  FIG. 7 is a schematic sectional view showing a plasma processing apparatus used for forming a fluorocarbon coating. FIG. 8 is a diagram showing the relationship between the distance (z) between the shower plate and the electrode of Ar plasma, Kr plasma, and Xe plasma and the electron density (ev) in the plasma processing apparatus of FIG.

  Referring to FIG. 7, the microwave passes through the insulator plate and the shower plate 23 below the radial line slot antenna (RLSA) 21 installed on the plasma processing apparatus 102 via the insulator plate. And emitted to the plasma generation region. Xe gas or Ar gas is blown out uniformly from the upper shower plate 23 to the plasma generation region through the gas introduction tube 13, and the plasma is excited by the microwaves radiated there.

  A lower shower plate 22 is installed in the diffusion plasma region of the microwave excitation plasma processing apparatus.

Here, if Kr, Xe, or Ar gas is flowed from the upper shower plate 23 and CxFy (C ₅ F ₈ , C ₄ F _8, etc.) gas is flowed from the lower shower plate 22, the base material (anodized film by a nonaqueous solvent) is used. as _Al to 2 _{O 3} AlMgCeZr alloy having a film) 14 of the _Al 2 _{O 3} film on the can formed of fluorocarbon film.

Oxygen gas or N ₂ / H ₂ or NH ₃ gas is used for oxidation or nitridation treatment, and O ₂ / NH ₃ or O ₂ / N ₂ O, O ₂ / NO gas or the like is oxidized in the case of an oxynitriding process. A mixed gas of a reactive gas and a nitriding gas may flow from the upper shower plate 23.

  The substrate 14 to be processed is installed in a processing chamber 24 where plasma is diffused and directly irradiated, and is oxidized by oxygen radicals excited by the plasma. At this time, it is desirable that the object to be processed be installed in the space where the plasma is diffused, not in the space where the plasma is excited, even in the processing chamber 24.

  Further, the exhaust gas in the processing chamber 24 passes through the exhaust duct via an exhaust port (not shown), and is led from one of the inlets to the small pump to the small pump.

  As shown in FIG. 8, when the distance (z) between the shower plate and the electrode is 30 mm or more, the electron density becomes substantially constant, and the electron density decreases in the order of Ar, Kr, and Xe.

As described above, in any case, Kr and Xe gases have lower electron cross-sections and smaller ionization energies when the electron density is lower than Ar. Therefore, when microwaves are irradiated to Xe (or Kr) gas, The electron density is reduced, damage to various films formed during film formation can be suppressed, and the etching action of C ₅ F ₈ gas can be suppressed.

  Referring to FIG. 9, the degas measurement system 103 includes a degas measurement device 30 and a photoion measurement device.

Light sample inside the heating furnace 40 of the ion measuring device (nonaqueous obtained by forming a CFx film on _{the Al} 2 _{O 3} film _{the Al} 2 _{O 3} film on AlMgCeZr alloy having a anodic oxide film by the solvent) 46 is disposed Yes. In the heating furnace 40, Ar as a carrier gas is adjusted to a flow rate of 100 sccm by the mass flow controller 44 as shown by an arrow 45 and introduced into the heating furnace 40 through the introduction pipe 47.

  The heating furnace 40 is provided with a heater 41 for heating and a photoion detector 42. The gas liberated from the sample 46 is introduced into the degassing measuring device 30 through a pipe 48 provided with a valve 53. Note that an exhaust pipe 52 provided with a valve 51 for exhausting branches off in the pipe 48.

  The degassing measuring device 30 is provided on the discharge electrode 32. The gas in the degassing measuring device 30 is connected to pipes 36a and 36b provided with vacuum pumps 37a and 37b, respectively. The pipes 36a and 36b merge to form an exhaust pipe 38, which is indicated by an arrow 39. To be exhausted. On the other hand, piping 34 and 35 are respectively provided in the portion where the degassing measuring device 30 and the discharge electrode 32 adjacent thereto are provided. The piping 34 is connected via the variable capacity control valve 61 and the mass flow meter 62a. As indicated by an arrow 63, the air is exhausted at a flow rate of 600 sccm. On the other hand, the pipe 35 is exhausted through the mass flow meter 62b at a flow rate of 550 sccm as indicated by an arrow 64, and the two pipes 34 and 35 are merged into a pipe 65 and exhausted as indicated by an arrow 66.

  The piping 33 of the degassing measuring device 30 is connected to the piping 33 provided with a mass flow controller 58 for introducing Ar gas at 1 SLM, as indicated by an arrow 59, at different peripheral positions of the same part in the length direction. ing. Further, a valve 53 is provided downstream of the exhaust pipe 52 of the pipe 48, and a pipe 56 provided with a mass flow controller 57 for introducing Ar gas for dilution at 500 sccm further downstream is a valve 54. Connected through. The pipe 48 is connected to a different position in the outer peripheral direction at the same position in the length direction as the part where the exhaust pipe 35 of the degassing measuring device 30 is provided.

  Next, a supplementary description will be given of the CFx film forming process using the apparatus shown in FIG.

Nonaqueous on the _Al 2 _{O 3} film of AlMgCeZr alloy having an _Al 2 _{O 3} film as an anode oxidation film by the solvent, by Ar plasma using a fluorocarbon gas as a reactive gas, forming a CFx film having a thickness of 0.01μm~10μm Film.

Here, as the fluorocarbon gas of the reaction gas, the unsaturated compound represented by the general formula C _n F _2n (where n is an integer of 2 to 8) or C _n F _2n-2 (n is an integer of 2 to 8). Aliphatic fluorides can be used, but fluorocarbons including octafluoropentine, octafluoropentadiene, octafluorocyclopentene, octafluoromethylbutadiene, octafluoromethylbutyne, fluorocyclopropene or fluorocyclopropane, Fluorocarbons represented by the general formula C ₅ H ₈ such as fluorocarbons containing butene or fluorocyclobutane are preferred.

  When the film is formed by Ar gas plasma, the dielectric constant of the CFx film is lowered, which makes it possible to make the dielectric constant of the CFx film as low as 1.7 to 2.2.

  After the CFx film is formed, plasma can be generated with a mixed gas of hydrogen and oxygen in the chamber to clean the inner wall of the chamber.

Further, after film formation or after annealing, surface nitriding of the CFx film is performed by Ar / N ₂ plasma. Thereby, degassing from the CFx film can be reduced.

  Preferably, annealing is performed after film formation. Annealing may be performed in the plasma chamber as it is without exposing the substrate to the atmosphere, or may be performed by another annealing apparatus. In any case, the atmosphere may be an inert gas atmosphere, and the pressure may be atmospheric pressure, but is preferably performed under a reduced pressure of about 133 Pa (1 Torr). Further, before or after annealing, the CFx film is preferably irradiated with Ar plasma.

The present invention, industrial materials used for AlMgZr alloy or AlMgCeZr alloy surface, _{the Al} 2 _{O 3} film was formed by anodic oxidation with a non-aqueous solvent, the material and it was further coated with fluorocarbon film to the _{the Al} 2 _{O 3} film surface Alternatively, the present invention relates to an industrial product and an electronic device manufacturing apparatus using the industrial material. As an electronic apparatus manufacturing apparatus according to an embodiment of the present invention, an air blocking type single wafer apparatus will be described below.

  In order to realize ultra-clean and completely controlled substrate processing in an air-blocking single wafer apparatus, an air-blocking and air-tight substrate processing apparatus having airtightness for controlling the atmosphere is required. This air-blocking hermetically sealed substrate processing apparatus has resistance to chemicals used in the cleaning process or gas generated during the process. Furthermore, in large-sized substrate processes, the weight of equipment members increases as the equipment becomes larger. Strengthening is required. The material according to the present invention sufficiently satisfies the requirements for such an air-blocking hermetic substrate processing apparatus.

  FIG. 10 shows a cross-sectional configuration of an air blocking sealed type cleaning apparatus as an example of the air blocking sealed substrate processing apparatus. Note that this air-blocking hermetic cleaning apparatus is an application of the present invention to the cleaning apparatus described in Japanese Patent Application Laid-Open No. 2007-88398 (Patent Document 7).

In this air-blocking hermetic cleaning apparatus, the fluorocarbon-alloy composite material shown in FIG. 11 having a three-layer structure according to the present invention is used for the outer wall of the apparatus. A cross section of the outer wall of the apparatus is shown in FIG. In FIG. 11, 71 is the inside of the apparatus, 72 is a fluorocarbon film or polymerized fluorocarbon film, 73 is a non-porous anodic oxide film (for example, an amorphous Al ₂ O ₃ protective film) by anodization with a non-aqueous solvent, 74 Is the above-mentioned Al-Mg-Ce-Zr alloy (or the above-mentioned Al-Mg-Zr alloy not containing Ce), and 75 is outside the apparatus. In the air-blocking hermetic cleaning apparatus, the fluorocarbon-alloy composite material shown in FIG. 11 may be used at least on the part of the outer wall of the apparatus that comes into contact with the corrosive liquid inside.

  Returning to FIG. 10, a configuration other than the above of the air-blocking hermetic cleaning apparatus will be described.

  The container 77 in which the substrate to be cleaned 76 is arranged is shielded from the outside air, and the atmosphere in the container is controlled by an atmosphere component measuring device 78, a gas supply unit 79 for controlling the atmosphere, and a gas discharge unit 80. The container 77 is a wet process container, and the container 77 has a configuration in which the internal space is sealed so as to block the atmosphere during the process.

  The atmosphere control parameters in the container 77 are arbitrary, such as temperature, pressure, and concentration. However, in order to suppress the formation of watermarks and natural oxide films and to maintain the flatness of the silicon surface, it is preferable to control the concentration of oxygen as an oxidizing species. As the atmosphere component measuring device 78, an oxygen concentration meter is optimal.

  The gas supply unit 79 employs a method of controlling the supply gas amount with a valve and supplying it into the container 77. The gas is preferably an inert gas such as nitrogen or argon, but the gas type can be arbitrarily selected according to the type of substrate to be cleaned 76 and the purpose of cleaning. Furthermore, it is not always necessary to use a single gas species, and a mixed gas may be used if necessary. The gas supplied to the container 77 is supplied to the surface of the substrate to be cleaned 76 in a uniform and laminar flow from the shower plate 81 arranged to face the substrate to be cleaned 76.

  The gas exhaust unit 80 can select either vacuum exhaust using a vacuum pump or gas exhaust for general exhaust. However, in order to perform efficient gas replacement in any exhaust, it is preferable to reduce the gas retention portion. As a specific countermeasure, there is a method of supplying air or an inert gas to a rotation holding mechanism (83 to 87) described later, but the retention portion reduction method is not limited to this. In order to realize a uniform flow of fluid, the exhaust ports are preferably arranged along concentric circles. By taking such a measure, the gas supplied from the shower plate 81 to the surface of the substrate 76 to be cleaned in a uniform and laminar flow can be smoothly exhausted in a uniform flow.

  The atmosphere in the container 77 is measured by the atmosphere component measuring device 78, and the pressure in the container 77 is measured and monitored by the pressure measuring device 82.

  A fixed shaft 83 is inserted from substantially below the center of the container 77, and a fluid bearing 84, a rotation support member 85, and a drive motor 86 are disposed around the fixed shaft 83. The rotation support member 85 is rotated by the drive motor 86, and the table 87 connected to the rotation support member 85 is rotated accordingly, whereby the substrate to be cleaned 76 is rotated. A portion including 83 to 87 is referred to as a rotation holding mechanism portion. During the rotation, it is the role of the fluid bearing 84 to make the operation of the fixed shaft 83 and the rotation support member 85 stable and smooth, and a fluid bearing such as a bearing is generally used. However, in the case of a bearing, it is difficult to prevent particles and outside air from being mixed due to mechanical friction of the bearing. Therefore, the fluid bearing 84 employs a combination of a magnetic fluid and a strong magnet used in a seal unit of a vacuum apparatus. . If this system is adopted, a fluid bearing having no dust generation and high sealing performance can be realized, and the above-mentioned problems can be overcome. Further, by supplying an inert gas to the rotation holding mechanism part (83 to 87) via the gas supply part 79 ', it is possible to contribute to prevention of gas diffusion through the magnetic fluid and reduction of the gas retention part.

  Next, the drainage separation mechanism in the air-blocking hermetic cleaning device of FIG. 10 will be described.

  A variety of wastewater such as acid / alkali / organic wastewater or concentrated / diluted wastewater is discharged in the cleaning process. If they can be separated and drained, it is possible to expect effects such as reduction of wastewater treatment amount and easy collection and utilization of chemicals.

  In this air-blocking hermetic cleaning apparatus, a plurality of cup-shaped guide walls 88 to 90 arranged concentrically are arranged in order to guide a desired cleaning drainage to each drain outlet. A drainage port led to a predetermined drainage system is disposed below the container 77 between the guide walls 88 to 90. An exhaust port 91 is also installed in the drain port installation part with a height difference.

  Drive motors 92 to 94 that move the guide walls 88 to 90 up and down are installed below the guide walls 88 to 90 via bellows (not shown). The drive motor is moved up and down to expand and contract the bellows. If the guide walls 88 to 90 are moved up and down, each desired washing drainage (drainage) can be guided to a desired drainage system.

  The method of supplying the cleaning liquid to the air-blocking hermetic cleaning apparatus in FIG. 10 is also extremely important. Cleaning liquids such as ultrapure water, chemical liquid, and functional water supplied to the air-blocking hermetic cleaning apparatus are supplied to the air-blocking hermetic cleaning apparatus through a supply pipe 95 from an ultrapure water / chemical liquid supply apparatus (shown later) outside the cleaning apparatus. Thereafter, the liquid is guided to the nozzle 97 through a supply pipe 96 disposed along a cleaning liquid ejecting arm (not shown), supplied to the surface of the substrate to be cleaned 76, and used for cleaning.

  Although the atmosphere control measures for the air-blocking closed type cleaning device have been described, control of the concentration, components, temperature, etc. of ultrapure water, chemicals, etc. supplied to the cleaning device is not possible no matter how much the atmosphere of the cleaning device is controlled. If it is sufficient, the air-blocking hermetic cleaning device cannot exhibit its ability. Therefore, gas-impermeable pipes described below are used as the supply pipes 95 and 96 of the air-blocking hermetic cleaning apparatus shown in FIG.

  With reference to FIG. 12, the supply method of the ultrapure water and the chemical | medical solution using gas impervious piping applied to the said air | blocking airtight type | mold sealing apparatus by one Embodiment of this invention is demonstrated. As shown in FIG. 13, the gas-impermeable pipe here includes an inner layer 301 formed of fluororesin (any one of ETFE, PTFE, FEP, and PFA) or PVDC (polyvinylidene chloride), and on the inner layer 301. And an intermediate layer 302 formed of nylon and an outermost layer 303 formed of fluororesin (any of ETFE, PTFE, FEP, and PFA) or PVDC on the intermediate layer 302.

  FIG. 12 shows a substrate processing system 200 for cleaning a substrate such as a semiconductor substrate or an FPD (Flat Panel Display) substrate. This substrate processing system 200 is used as the substrate processing apparatus in the air-blocking hermetic cleaning apparatus of FIG. A corresponding cleaning chamber 201 is included. That is, the cleaning chamber 201 functions as the air-blocking hermetic cleaning device shown in FIG. The basic configuration of the substrate processing system 200 is the same as that described in Japanese Patent Application Laid-Open No. 2007-287876 (Patent Document 8).

The basic configuration of the substrate processing apparatus 201 includes processing liquid input ports 202, 203, and 204 connected to a processing liquid supply source, where 202 is an input port for introducing ultrapure water, 203 is an input port for introducing a chemical liquid, Reference numeral 204 denotes an input port for functional water. Each port has a resin pipe having an oxygen permeability coefficient of 5 × 10 ⁶ [piece · cm / (cm ² secPa)] or less, preferably 2 × 10 ⁶ [piece · cm / (cm ² secPa)] or less. Gas impermeable piping) 205, 206, and 207 are connected to each other, and each of the resin piping 205, 206, and 207 is connected to the nozzle 208. From the nozzle 208, at least one of ultrapure water, chemical solution, and functional water transported by the resin pipes 205, 206, and 207 is discharged to the substrate to be processed 209 held on the turntable 210, and the surface of the substrate 209 is discharged. A cleaning process is performed.

The chemical / functional water / ultra pure water supply device 211 has a deaeration device 212, valves 215-1 to 215-6, an oxygen permeation coefficient of 5 × 10 ⁶ [piece · cm / (cm ² secPa)] or less, preferably Resin piping (gas impervious piping) 217-1 to 217-3, 218-1 to 218-3, 219-1 to 219-2 that is 2 × 10 ⁶ [pieces / cm / (cm ² secPa)] or less I have. The ultrapure water is introduced from the resin pipe 217-1, deaerated by the deaeration device 212, led out from the resin pipe 217-1 through the resin pipe 217-1 and the valve 215-1, and the valve 215-2. It can also be used for mixing with chemicals. The necessary types of chemicals are deaerated from the resin pipe 218-1 by the deaerator 212 and mixed with ultrapure water through the valve 215-3 or 215-4 and the resin pipe 218-2. The degassed / prepared chemical liquid is led out from the resin pipe 218-3 through the valve 215-5. The functional water is led out from 219-2 through the resin pipe 219-1, the valve 215-6 and the resin pipe 219-2. The ultrapure water, chemical liquid, or functional water derived from the chemical / functional water / ultra pure water supply device 211 has an oxygen permeability coefficient of 5 × 10 ⁶ [piece · cm / (cm ² secPa)] or less, preferably 2 The processing liquid input ports 202, 203, and 204 of the substrate processing apparatus 201 are passed through resin pipes (gas-impermeable pipes) 220, 230, and 240 that are not more than × 10 ⁶ [pieces / cm / (cm ² secPa)]. And the substrate processing apparatus 201 is supplied with ultrapure water, chemical solution, and functional water, respectively.

In the example of the figure, resin pipes 220, 230, and 240, which are pipes between apparatuses 211 and 201 (inter-apparatus pipes), are exposed to clean room air, but these inter-apparatus pipes 220, 230, and 240 are 5 ×. 10 ⁶ [pieces / cm / (cm ² secPa)] or less, preferably 2 × 10 ⁶ [pieces / cm / (cm ² secPa)] or less, because resin piping (gas impervious piping) is used. It is possible to prevent oxygen from being mixed into the ultrapure water and / or the chemical solution and / or the functional water, and to prevent the adverse effect of oxygen in the substrate processing in the processing apparatus 201 to the limit.

On the other hand, the substrate processing apparatus 201 and the supply apparatus 211 normally take in clean room air through a filter such as HEPA, but the resin piping 205, 206, 207, 217-1 to 217-3, 218-1 to 218 inside the substrate. -3, 219-1 to 219-2 also have an oxygen permeability coefficient of 5 × 10 ⁶ [piece · cm / (cm ² secPa)] or less, preferably 2 × 10 ⁶ [piece · cm / (cm ² secPa)] Since the following resin pipe (gas impervious pipe) is used, it is possible to prevent oxygen from being mixed into the deaerated ultrapure water and / or chemical liquid and / or functional water. In the case where nitrogen gas is introduced with one or both of the substrate processing apparatus 201 and the supply apparatus 211 as a sealed structure, the conventional resin pipe can be used, but the above-described gas-impermeable pipe. It is more preferable to use resin piping for the following reason.

  That is, by reducing the number of gaseous gases that do not want to be dissolved around the pipe and using a pipe that is difficult to permeate the gas, the rate at which the gas diffuses through the pipe and dissolves in the liquid itself decreases, and the amount of dissolution is reduced. Further reduction can be achieved. That is, the effect is further increased by suppressing the rate at which the pipe dissolves the gas and further reducing the amount of gas dissolved by the atmosphere replacement by introducing nitrogen gas. In addition, by reducing the gas dissolution rate using the resin pipe which is the gas impervious pipe, the amount of gas used to replace the atmosphere in the apparatus is reduced, and it is not necessary to increase the sealing degree of the apparatus. Management concentration can be made easy. Furthermore, from the same viewpoint, if the inter-apparatus pipes 220, 230, and 240 are accommodated in a sealed body and nitrogen gas or the like is introduced, the dissolved amount of oxygen can be further reduced.

  In addition, even if the piping is exposed to a harsh atmosphere such as a cleaning chemical solution such as hydrofluoric acid, the outermost layer is a chemical solution as long as it is a resin piping that is the above gas-impermeable piping adopting fluororesin or PVDC on the outermost surface. Will not be eroded by.

  In the substrate processing apparatus 201 or the supply apparatus 211 shown in the figure, all the pipes are formed by the resin pipes that are the gas impermeable pipes, but only a part of the pipes are formed by the resin pipes that are the gas impermeable pipes. It may be formed.

Ce alloy-added Al alloy (4.5% Mg-0.1% Zr-Al) and Ce alloy-free Al alloy (4) used as a container structure of an electronic device manufacturing apparatus according to an embodiment of the present invention It is a figure which shows the Vickers hardness of 0.5% Mg-0.1% Zr-Al). Relationship between Ce concentration (mass%) added to 4.5% Mg-0.1% Zr-Al alloy sample and Vickers hardness, and 4.5% Mg-0.1% Zr-Al alloy sample It is a figure which shows the relationship between Ce density | concentration (mass%) added with respect to Vickers hardness increase rate (%). Weight loss after a sample of anodized 4.5% Mg-0.1% Zr-Al alloy with Ce added was sealed at 100% Cl ₂ and 0.3 MPa and exposed at 200 ° C. for 6 hours. It is a figure which shows a rate. It is a diagram for explaining a method of forming a fluorocarbon film on the surface (AlMgCeZr alloy having an _Al 2 _{O 3} film as an anode oxide film formed by the non-aqueous solvent) substrate. Is a diagram showing a result of the polymerization fluorocarbon film formed on the Al ₂ O ₃ film on the AlMgCeZr alloy by the above method were analyzed by X-ray photoelectron spectrometer. It is a figure which shows the scanning electron microscope image before and after immersion for 24 hours to the 5 wt% hydrofluoric acid-hydrogen peroxide water mixed solution of the said polymeric fluorocarbon film. It is a schematic sectional drawing which shows the plasma processing apparatus used in performing another formation method of a fluorocarbon film. It is a figure which shows the relationship between the distance (z) between the shower plate and electrode of Ar plasma, Kr plasma, and Xe plasma in the plasma processing apparatus of FIG. 7, and an electron density (ev). It is a diagram illustrating a degassing measurement system samples 46 forming a CFx film on _{the Al} 2 _{O 3} film on AlMgCeZr alloy having an _Al 2 _{O 3} film as an anode oxidation film by the non-aqueous solvent is disposed. It is sectional drawing used for description of the electronic device manufacturing apparatus by one Embodiment of this invention. It is sectional drawing of the apparatus outer wall of the apparatus shown in FIG. It is a figure for demonstrating the supply method of the ultrapure water and chemical | medical solution using the gas impervious piping used in this invention. It is a figure for demonstrating the gas impervious piping in FIG.

Explanation of symbols

71 Inside the device 72 Fluorocarbon film or polymerized fluorocarbon film 73 Anodized film 74 AlMgCeZr alloy 75 Outside the device

Claims (11)

  In an electronic device manufacturing apparatus using an Al alloy member as at least a part of a container, at least a part of the surface of the Al alloy member is covered with a nonporous anodic oxide film made of a nonaqueous solvent, and the anodic oxide film is An apparatus for manufacturing an electronic device, wherein the apparatus is covered with a fluorocarbon film or a polymerized fluorocarbon film, and the at least part of the surface of the Al alloy member is a part that comes into contact with a corrosive liquid.   In the electronic device manufacturing apparatus using an Al alloy member for at least a part of the container, the Al alloy member includes Mg, Zr and Ce in mass%, and the Mg concentration exceeds 0.01% and is 5.0% or less. Ce concentration is more than 0.01% and not more than 15.0%, Zr concentration is more than 0.01% and not more than 0.15%, the balance is made of Al and inevitable impurities, and the elements of the inevitable impurities are each 0 0.01% or less, and at least a part of the surface of the Al alloy member is covered with a nonporous anodic oxide film made of a nonaqueous solvent, and the anodic oxide film is covered with a fluorocarbon film or a polymerized fluorocarbon film. An electronic device manufacturing apparatus.   The Al alloy member contains Mg, Zr and Ce in mass%, Mg concentration is over 0.01% and 5.0% or less, Ce concentration is over 0.01% and 5.0% or less, and Zr concentration is 3. The electron according to claim 2, wherein the content is more than 0.01% and 0.15% or less, the balance is made of Al and inevitable impurities, and the elements of the inevitable impurities are each 0.01% or less. Equipment manufacturing equipment.   4. The electronic device manufacturing apparatus according to claim 2, wherein the at least part of the surface of the Al alloy member is a portion that comes into contact with a corrosive liquid.   5. The electronic device manufacturing apparatus according to claim 2, wherein a thickness of the anodic oxide film is 0.01 μm to 0.6 μm. The electronic device manufacturing apparatus according to claim 1, wherein the anodic oxide film is an amorphous Al ₂ O ₃ film.   The electronic device manufacturing apparatus according to claim 1, wherein the fluorocarbon film or the polymerized fluorocarbon film has a thickness of 0.01 μm to 10 μm.   8. The container according to claim 1, wherein the container is a container for a wet process, and the container is configured to be sealed so that the internal space blocks the atmosphere during the process. Electronic device manufacturing equipment. A resin pipe for supplying a chemical solution or pure water to the container is further included, and the resin pipe has an oxygen permeability coefficient of 5 × 10 ⁶ [piece · cm / (cm ² secPa)] or less. Item 9. The electronic device manufacturing apparatus according to any one of Items 1 to 8. 10. The apparatus for manufacturing an electronic device according to claim 9, wherein the oxygen permeability coefficient of the resin pipe is 2 × 10 ⁶ [piece · cm / (cm ² secPa)] or less.   The resin pipe has an inner surface formed of any one of ETFE, PTFE, PVDC, FEP, PFA, and an outer surface formed of any one of ETFE, PTFE, PVDC, FEP, PFA. The electronic device manufacturing apparatus according to claim 9, further comprising a layer formed of nylon in the middle.