TW561514B - Member for semiconductor manufacturing system and its manufacturing method - Google Patents

Abstract

A technique of forming a composite oxide coating film excellent in metal-contamination resistance and corrosion resistance to, e.g., hydrofluoric acid and hydrochloric acid on the surface of a member for a semiconductor manufacturing system is provided. A slurry of silicon oxide-aluminum oxide-chromium oxide and a sintering aid for producing an amorphous inorganic substance by sintering is applied to the surface of the base, and the base is heated and baked at 250-750 DEG C to form a composite oxide coating film and to form a deposit layer of amorphous inorganic particles by using a chromium oxide aqueous solution containing a sintering assistant.

Description

561514 V. Description of the invention (1) ----- " " [Technical field to which the invention belongs] The present invention relates to a semiconductor manufacturing device, for example, as a wafer heat treatment device and an oxidation-diffusion treatment device, a CVD device, Components used in the construction materials of various devices such as cylinders (gas cylinders), gas supply piping, exhaust chute of reactor devices, exhaust gas treatment devices, etc., and their manufacturers 2 ° In particular, for gaseous corrosive gases A technology that forms a composite oxide film with excellent resistance to metal contamination during processing under high vacuum, while remaining excellent in halogen-based compounds and the like. [Prior art] In many cases, a semiconductor element is manufactured by forming a film, such as a wiring and an insulating layer, on a silicon wafer. As a device for manufacturing the semiconductor device, an oxidation-diffusion processing device, a CVD device, and the like are exemplified. The aforementioned oxidation-diffusion treatment device is an oxidation forming treatment for forming an oxide film port on a silicon wafer by mixing hydrogen and oxygen to form water vapor or introducing hydrogen and HC1, etc. in a reaction vessel, and performing phosphorus and boron Packing such as the diffusion of impurities, $. The second CVD device is a device that introduces several kinds of reactive gases into a processing furnace and generates a desired film on a chemical stone wafer in a temperature range of 300 to 1000 ° C. These devices process the components of the reaction container of the Shixi wafer, and use quartz such as quartz = and metal materials. "Although the use of metals is excluded, all of them make it difficult to use non-metallic inorganic materials, which is also disadvantageous to costs. Among the eight-capacity / mechanical / components, in the past, non-dynamic steel (SUS316L) 4 was used to form a non-dynamic coating of chromium on the surface of the material.

this. For example, 'hard steel consisting of fine particles of chromium trioxide (Cr 03), which is not recorded in steel, is shown in JP 5 9 _ 9 1 7 1, JP 2 6 6 8 2, and JP-A Zhao oxide system. The non-dynamic skins are adequate. The reason is that metal contamination is caused by the treatment of the film-forming process. In the case of special gases, the formation of chromic acidity is low due to the excellent contamination caused by halogen-based metal materials such as chlorine trifluoride gas, which can be regenerated by contact with low-pressure decompression. Expect 561514 5. Description of the invention (2) As the material in contact with the atmosphere gas i The surface of the substrate 'the technique of forming a chromium dioxide (Cr2O3) film by chemically changing chromium oxides' is disclosed in Japanese Patent Laid-Open No. 6 1 _ 5 2 3 7 4, Japanese Patent Laid-Open No. 6 3-1 63-317680, and the like. However, the characteristics of the film's tolerance to substrates disclosed in these publications and the conditions such as the temperature of the matrix material (stainless steel) of these elements are attached to silicon wafers, and it has been confirmed that In the case of reductive rotten gases such as hydrogen and ammonia, and in the case of cleaning with a voxel-based compound, the dye is increased. However, stainless steel is regarded as =, and its surface, by contact with the atmosphere, moves the film. This non-dynamic film, due to the erosion caused by the original thick conflict, and the self-repairing effect with the acid solution, etc., has a non-active film. However, this is a chemical reaction time for regeneration. In particular, it is impossible to make 2053-5291-PF (N) because it constitutes g μ Μ f, -ρ, ^ mattress + conductor manufacturing and placing the door under the condition of interactive exposure to the atmosphere and :: body. Ahddub.ptd Metal materials and materials (Cr2 03) are not easy to be destroyed by particles, due to the characteristics of nature. In terms of the long part, the effect of the atmosphere and the degree of reaction is 561514. V. Description of the invention (3) Better than t Γ 2 The purpose is to obtain a + conductor with excellent corrosion resistance and metal pollution resistance. Technology for manufacturing device components. [In the invention, we found that the oxide skin was strong. That is, the steel substrate is a sintering agent, and the method is based on the sintering agent: after the sintering agent, it is described by chromium monoxide, ① a layer in the gap of the pre-sintering agent]. As a result of careful research, if the inventors covered the surface of the metal material with a chemically stable compound, it would not only inhibit the release of metal atoms from the substrate, but also develop effective corrosion resistance in a corrosive environment. This article is made of chromium and alumina made from chrome, and its special cloth contains oxidized aluminum in solution. The particles are internal particles. The present invention is on the surface of a semiconductor manufacturing device. It is formed by coating a composite oxide film composed of silicon oxide-alumina-oxide. The present invention relates to a surface of a steel substrate of an element for a semiconductor manufacturing device, which is coated with a raw material containing oxidized particles, and then formed into a chemically densified skin by sintering. Then, chromic acid is coated on the surface of the chemically densified film. Water / valley fluid is formed by spraying or immersing in the water at 250 ° C ~ 750 ° C to form a composite oxide film composed of oxidized stone and sintering and 纟 ° s 彳. In the present invention, the composite oxide film is formed by chemically densifying a film composed of silicon oxide and oxygen, and an amorphous complex oxygen covering the surface of the film while filling it.

561514 V. Description of the invention (4)

② The aforementioned composite oxide film is coated with raw materials containing oxidation and sintering aids. On the chemical densification inscription obtained by sintering, it is coated with an aqueous solution containing chromic acid and sintering aids, and sintered with a reverse film at ~ 750 ° C. Precipitation in the voids in the substrate and on the surface of the substrate C = amorphous inorganic composite composite particles composed of sintering aids = chromium = f The aforementioned sintering aids are selected from borate compounds and phosphate compounds at least] -text- The present invention proposes another feature of the present invention, which is characterized in that on the steel base / ~, there is an amorphous material composed of chromium oxide and a sintering aid: ": 'an element for a semiconductor manufacturing device characterized by an out layer铖 The analysis of particles is also a method of the present invention. A semiconducting method is applied to the surface of a steel substrate to apply the manufacturing liquid of the components for layout, spray, or immerse in the chromic acid:; The characteristic is that after that, by forming a chromic acid layer in ㈣. ^ /, Its special chromium and sintering aid are composed of non-C / degree sintering to form oxygen. In the present invention, the former Precipitation layer ; 2 It is made from a phytate compound and Shi Xi is sintered to produce an amorphous inorganic substance; and is seeded 'and the knot [Embodiment] The following is a detailed description of the nature (low metal emission) I = resistance In particular, it is a metal-contaminated bovine body manufacturing device element, especially 2053-5291-PF (N); Ahddub.ptd page 9 561514 5. Description of the invention (5) is a composite oxide coated on the surface of a steel substrate The structure of the film_ The first embodiment of the present invention is that the surface of the substrate using stainless steel (SUS316L) is coated with oxidized stone (Si02)-oxide name (Ai2〇3)-chromium oxide (C q 〇3 ) And a composite oxide film composed of a sintering aid, manufactured through the process shown in Figure 1. First, the stainless steel substrate for the semi-cold body manufacturing device is applied with degreasing and sandblasting (spraying with Oxidation—Etc.) Before treatment, then, on the surface of the crude steel substrate 'coated with raw material containing base layer', heated to a temperature of 4500t at a heating rate of 500C / h and maintained for! Hours, It is then cooled at a cooling rate of 20G, / h ~. By this treatment, the surface of the substrate A chemically densified film is formed. Technician: y group, on the chemically densified film, an amorphous inorganic substance is generated by under-sintering treatment, and the agent solution and the chromic acid solution are mixed.兹 山 a: 3 ,,,, σ 助, #_ 义 = of this σ, syrup, straw is sprayed or immersed in the ^ / syrup, the composition of the ingredients described in the formula, after that, by using the same as The above-mentioned M is combined into a composite oxide film suitable for the present invention. Solution: Example 2 Contains: Substances: Two: Water glass, salt glass and · =: which are good for sintering agents, it is better to use acetic acid to form ^, The coating impregnation and sintering of the above-mentioned mixed aqueous solution are repeated several times. According to the experiments of the inventors, the preferred sintering complex acid: the aqueous solution of the acid salt compound and the complex acid water, the heating temperature is 55Gt ~ mi, and coating chromium is applied. Acid water m 2053-5291-PF (N); Ahddub.ptd page 10 561M4 V. Description of the invention (6) The acidic compound was mixed at a temperature of 0.5 and the heating temperature was 250. 〇550 The water contained in the aqueous solution is steamed at a controlled time. After such a treatment, the amorphous layer of chemical particles with a particle size of about 3 is generated at the same time as chromium oxide containing the heating residue and dispersed. The sintering composed of this chromium oxidation and sintering aid == densified film, that is, it is precipitated in the space between si〇2—Αι203 and is chemically densified such as pores and cracks in the densified film At the same time as the surface of 臈 (including / text), such as before coating into ChOJ chromium dioxide), into. That is, chromic acid undergoes an intermediate salt compound, phosphatization: a borate compound present, a silicic acid inorganic substance. / Valley fluid releases water to become amorphous, the compound salt compound formed by the above aqueous solution + oxygen layer, the acid salt compound of the acid activator, the acid compound S, S, and A Either, but they will be amorphous and temporarily 5 sigma and glassy, and will precipitate (impregnate) in the pores and cracks in the chemically densified film and invade (impregnate), and their voids will become filled. State. The thickness of such a composite oxide film is preferably 40%. The aforementioned sintering aid has a function of increasing the adhesion between particles constituting the film. That is, amorphous materials are formed by sintering of rotten salt compounds, oxalate compounds, and salt-filling compounds.

2053-5291-PF (N); Ahddub.ptd Page 11 561514 V. Description of the invention (7) At the same time as the bond between the Cr203 fine particles precipitated from the raw material containing chromic acid, the chemical Cracks and densifies the membrane. In addition, the temperature range of these components' from normal temperature to 750 ° C has a strong affinity with oxygen and is very thermodynamically stable. Also, the aforementioned composite oxide film is formed by heating and sintering from the above-mentioned various raw materials and the starting materials of the water / valley shape. Its surface is smooth, its relative surface area is small, and it can become a pore. Small and dense membrane structure. Oxidation · a diffusion device and cVD device and other related semiconductor manufacturing devices or components used in the above-mentioned composite oxide film are usually cleaned in the maintenance device. 'Because of its chemical stability with respect to fluoric acid and environmental barrier properties, it is possible to prevent the infiltration of an aqueous fluoric acid solution for cleaning into the composite oxide film. Table 1 illustrates the conditions for forming a composite oxide film on the surface of a steel substrate with the conditions related to the present invention. (Table 1) Composite oxide film 'Main component ^ Sintered raw material Si〇2 / Al2〇3 particle raw material + 〇Γ2 03 aqueous solution ^ --- Implementation of the agent C "2 03 aqueous solution implementation C" 2. 3 water solution + borate compound solution, silicate phosphate compound solution, and FIG. 2 shows an example of the surface structure of the part covered with the composite oxide film related to the present invention. Here, c on the way is the composite oxide film, 1 is the base material of non-recorded steel, 2 is chemically induced, chemical film, 3 is filled with composite oxygen

2053-5291-PF (N); Ahddub.ptd Page 12 561514 V. Description of the invention (8) The pores in the chemical compound film C and the chromium oxide-amorphous sintering aid inorganic composite fine particles in the cracks, 4 is covered in A layer of chromium oxide-amorphous sintering aid-inorganic composite fine particles on the surface of the composite oxide film. In addition, it can be clearly found from the structure diagram of the loading surface that the above-mentioned layer of the chromium oxide-amorphous sintering aid inorganic composite fine particles is completely filled in the cracks of the composite oxide film of the fine particles. Extremely high environmental opacity. The second embodiment of the present invention replaces the method of forming a coating on the surface of a substrate (the first embodiment). 'The above-mentioned S102-AW-Cr203 is formed by a method of forming an inorganic substance film as described below, and Composite oxide film composed of sintering aid. That is, the characteristic of this embodiment is that the chromic acid aqueous solution containing a sintering aid is coated on the surface of the stainless steel substrate, sprayed or immersed in the chromic acid aqueous solution to form a chromic acid layer. By 25. (: ~ 75 ° It is sintered at a temperature of 'by forming a precipitation layer of amorphous particles of amorphous chiral material composed of chromium oxide and a sintering aid, which is so-called, on the surface of a non-steel substrate ^, which has chromium oxide and Method for obtaining an element for a semiconductor manufacturing device by sintering a composition of a sintered amorphous substance fine particle precipitation layer 0 As in the second embodiment, the aforementioned amorphous inorganic substance such as oxide complex particles is directly provided on the surface of the substrate. Brother of the precipitation layer of fine particles. If it is possible to form the complex compound oxide film as compared with the first embodiment, it can simplify the construction method, shorten the shrinkage during manufacturing, and reduce the manufacturing cost. And 'the precipitation layer thus obtained not only brings

2053-5291-PF (N); Ahddub.ptd Page 13 561514 V. Description of the invention (9) Enhanced thermal shock resistance, practical rules for changing properties ^ Corrosion resistance and metal contamination resistance for clever purposes < Implementation is also very full. [Example] I Example 1: In this example, a semiconductor oxide film formed by applying the compound of the present invention :::: formed on a part in contact with the gas x is formed. The device (CVD device) was used for heat treatment to investigate the effect of metal contamination on the silicon wafer. (1) The composite oxide film of the example of the present invention: on the inner surface of the substrate (SUS316L: pipe with an outer diameter of 300 mm × thickness 0.9 mm), a raw material containing silicon oxide, aluminum oxide and phosphoric acid is applied, and heated Sintering to form a chemically branched film thickness, immersing the element to which the chemically densified film is attached is immersed in an aqueous solution containing chromic acid and phosphoric acid as the main components, and after pulling up, heat treatment is performed at 450 ° C for 1 hour. Repeat 6 times, using the formed composite oxide film (80 / m). (2) The material of the comparative example is an untreated SUS316L steel substrate. Result of metal contamination quantity evaluation test: This test is to measure the amount of metal contamination on the Shixi wafer using the apparatus ′ of FIG. 3. The results are summarized in Table 2. As shown in Table 2, when using the untreated SUS316L steel material of the comparative example, the metal contamination amount of the silicon crystal circle was Fe: 3.9x1012atm / cm2, Cu: 3.1χ1012atm / cm2. In contrast, on the substrate coated with the composite oxide film suitable for the present invention, it is reduced to F e: 3. 1 X * 1 09 a t m / c m2, Cu: 7.8 x 109 atm / cm2.

2053-5291-PF (N); Ahddub.ptd Page 14 561514 V. Description of the invention (ίο) (Table 2) Metal compound S 1 on silicon wafers atm / cm2 Fe Cu The present invention is provided with a composite oxide film SUS316L material 3.1χ1〇9 7.8χ109 Comparative example SUS316L material without treatment 3.9χ1〇ΐ2 3.1x10 ^ 2 ~~ Detection side limit 8x1 〇8 δχΐ〇8 Example 2: In this example, it is intended to apply to this The substrate with the composite oxide film obtained from the treatment related to the invention was washed with an acidic aqueous solution, and the substrate was immersed in 10% hydrochloric acid for 24 hours, and the acidic acid aqueous solution was tested from the mass change before and after. Sex. In addition, the untreated Su § 3 16 L steel of the comparative example had a significant mass loss due to dissolution, and the immersion time was 1 hour. The results of this test are shown in Table 3. As shown in Table 3, it is clear that the quality change of the composite oxide film element related to the present invention is comparable to that of Shi Yangcai and shows excellent narrative resistance. (Table 3) Sample quality after immersion in 10% hydrochloric acid [(%) Uncommented with composite oxide film element U.006 Comparative Example 1 SUS316L steel 0.15 — 2 Quartz 0 — 01 — Example 3: On the surface of the same SUS316L stainless steel as in Example 1, a chromic acid water / valley solution containing a sintering aid composed of a phosphate compound and the like was applied to protect the base material of the sintered amorphous inorganic material film. | Investigate. The test is to make it completely immersed in 10% [1 (: 1 aqueous solution of 20 ° C) to investigate the appearance change and weight change before and after the test. For comparison,

2053-5291-PF (N); Ahddub.ptd Page 15 561514 V. Description of the invention (11) The same test was also performed on SUS316L steel after roughening and SUS316L after air-baking, and the results are shown in Table 4. As shown in Table 4, in the example of the present invention, a mass of about 176 mg, which can be said to be a part of the film, was reduced. However, in contrast, in the comparative example, the substrate was completely corroded, and all had a mass reduction of more than 20 mg. Therefore, it has been found that even on the surface of the base material, even when an amorphous inorganic material film mainly composed of chromium oxide is formed, the effect is expected. [Table 4] Sample quality S, S, S (9) mm / m color of the liquid sample reduced after 60 hours after the ω level was intact. S (9) Hydrochloric acid water, the color sm surface of the liquid solution || K / fK ηλΜ Example 1 of the present invention SUS31SL rim fired after coating with a chromic acid aqueous solution 56.93 $ No abnormality 56762 Stained-color film 17 $ Comparative example 2 SUS316L with WA · roughened 锎 52.957 Abalone no abnormality 52.725 Strong yellow縦 Comprehensive corrosion 232 3 500t-1h SUS316L refining in the air | 55.335 No abnormal 55.039 Concentrated yellow eagle full rot life 296 [Industrial applicability] According to the invention described above, as a component of a semiconductor manufacturing device, By using a device covered with the composite oxide film and the like unique to the present invention, the amount of metal released from the surface of the device is significantly reduced, and the metal contamination of the silicon wafer is also significantly reduced. In addition, the device can be cleaned with an acidic aqueous solution of the components of the device to increase the cleaning and maintainability of the device. Moreover, the components made from quartz components in the past can be converted to the composite oxide with the present invention.

2053-5291-PF (N); Ahddub.ptd Page 16 561514 V. Description of the invention (12) The possibility of cost-saving and easy operation and maintenance of the element of the film, for semiconductor manufacturing equipment and related equipment The element can be expected to expand the application field of the present invention. 2053-5291-PF (N); Ahddub.ptd Page 17

II

Claims (1)

561514 6. The scope of the patent application base material, cementitious group 2. Among them, the layer in the sintering agent gap is shaped 3. Among them, and the sintering coating contains sintering, sintering qi 4. Among them, and the sintering coating contains sintering, Sintering Qi 5. Compounding with a component salt to form a compound on a non-half surface is completed at the same time as the application of the aforementioned compound. If the application of the aforementioned sizing agent has chromic acid in the substrate composition, as in the application of the aforementioned sizing agent, there is chromic acid in the substrate composition, as shown in the application, and the substance and crystal are not patented. Interstitial amorphous patents combined with oxidized raw materials, rain-assisted internal interstitial amorphous patents, the aforementioned phosphate machine material conductors are used to make devices, #characterized in that they are made of steel and are emulsified with stone -Oxidation complexes are formed with oxide skins. Tansuke ^ The element for semiconductor manufacturing devices in the scope of patent No. 1, the oxide film is densified by oxidizing chemically, and the space within the non-skin ¥ filling and covering the surface of the film < non- The element for the semiconductor manufacturing device of the first item surrounded by the chrome lice compound particles is coated with a chemically densified coating film containing silica alumina and sintered at 250 ° C. 75 (TC and substrate | substrate | surface are formed by precipitating oxide complexes and auxiliary inorganic compound fine particles. The device for semiconductor manufacturing devices according to item 2, the coating film is coated with oxidized hair and oxidized aluminum to obtain the sintered On the chemically densified film, the aqueous solution of the binder is formed by precipitating the composite fine particles of chromium oxide and the auxiliary inorganic substance at 250 ° C (~ 750 ° C) and on the surface of the substrate. The sintering agent for the + conductor manufacturing device of item 3, or 4 uses at least one kind of material selected by sintering from a borate compound and a silicic acid compound. 2053-5291-PF (N); Ahddub.ptd Page 19 561514 6 · —Semiconductor: After the raw material of the sintering aid of the steel substrate, the chemically dense aqueous chromic acid solution is sprayed with 2 50 ° C ~ 75 0 ° C Composition of sintering and sintering aids 7 · If a patent application method is used, in which the former compound and the dish salt are formed into an amorphous inorganic substance 8 · — on the surface of a semiconductor substrate, Crystalline inorganic substance 9 · According to the patent application, the method for manufacturing a device for a main device for manufacturing an amorphous inorganic substance in a phosphate compound and the aforementioned sintering aid is characterized in that the surface is covered with silicon oxide, alumina, and Sintering forms a chemically densified film. The surface of the film is coated with a sintering aid-containing agent or immersed in the aqueous solution. The silicon oxide-alumina and chromium oxide are used to restore the & oxide film. . The scope of the 6th item "Donal" ^ Sintering is called sintering of conductor manufacturing device components, and it is a material of yttrium in phosphonate compounds and silicate compounds. At least one kind of device for manufacturing by sintering-* It is composed of ^, which is characterized by the sintering of steel micropores and sintering aid composition. 8th member > $ & ^ The first half of the body is used to make nightmares, and the agent is selected from at least three weathering materials and silicate compounds. A kind of semiconductor manufacturing device composed of a kind and produced by sintering, is: a surface 70, a method for manufacturing a piece on a steel substrate, which is characterized in that it is sprayed or immersed in an aqueous solution, and the coating contains After the chromic acid of the sintering aid, by forming a chromic acid layer in 25 (rc ~ 75 (rc sintering, aqueous solution), an amorphous inorganic substance composed of micro-formation is formed * by chromium oxide and sintering aid n. Precipitation layer of patent scope No. 1 (IS). Element for semiconductor manufacturing equipment of 10 items