Corrosion-resistant member

Abstract

Provided is a corrosion-resistant member that does not tend to react with hydrogen chalcogenide even at high temperature and does not tend to generate chalcogen-containing substances. The corrosion-resistant member is provided in a passivation device having a reaction vessel for performing passivation using a hydrogen chalcogenide gas and forms a portion of the reaction vessel that is in contact with the hydrogen chalcogenide gas. The corrosion-resistant member has a sintered body containing at least one selected from oxides of aluminum, nitrides of aluminum, oxides of zirconium, nitrides of zirconium, oxides of silicon, nitrides of silicon, and nitrides of boron, and the total proportion of oxides of aluminum, nitrides of aluminum, oxides of zirconium, nitrides of zirconium, oxides of silicon, nitrides of silicon, and nitrides of boron in the sintered body is more than 90 mass%.

Description

Corrosion-resistant materials

[0001] The present disclosure relates to corrosion-resistant members.

[0002] In recent years, in the field of semiconductors, semiconductor materials containing elements other than silicon (Si) have been attracting attention. Examples of semiconductor materials containing elements other than silicon include semiconductor materials containing III-V group elements such as germanium (Ge) and indium gallium arsenide (InGaAs), and semiconductor materials containing metal chalcogenides. Although these semiconductor materials have the advantage of higher mobility compared to silicon materials, they can sometimes be difficult to form into films or can have a high defect density at the interface between materials.

[0003] Therefore, in order to reduce the defect density at the interface between materials, a method has been proposed in which a passivation film is formed on a substrate of germanium, molybdenum, or the like using hydrogen sulfide (HS) gas (see, for example, Patent Document 1). Also, as a method for forming a metal chalcogenide film, a method has been proposed in which a molybdenum oxide layer or a tungsten oxide layer is treated with hydrogen sulfide gas to form a molybdenum sulfide layer or a tungsten sulfide layer (see, for example, Patent Document 2).

[0004] Japanese Patent Publication No. 2016 No. 207789 Japanese Patent Publication No. 2017 No. 61743 Japanese Patent Publication No. 2011 No. 189338

[0005] In the above-described method for reducing the defect density at the interface between materials, the reaction for forming a passivation film is performed at high temperatures, which can cause the inner surface of the reaction vessel in the passivation apparatus to react with hydrogen chalcogenide. As a result, chalcogen-containing materials produced by corrosion or decomposition of the material forming the inner surface of the reaction vessel can adhere to the inner surface of the reaction vessel. When passivation of a substrate such as a wafer is performed using a passivation apparatus with chalcogen-containing materials attached to the inner surface of the reaction vessel, the chalcogen-containing materials may adhere to the substrate when the reaction vessel is evacuated and replaced with an inert gas. Furthermore, the chalcogen-containing materials may adhere to the substrate, which can degrade the performance of the manufactured semiconductor structure.

[0006] For example, Patent Document 3 discloses a technique for cleaning substrates using a plasma cleaning apparatus. In this technique, sulfur-containing substances derived from sulfur hexafluoride gas used for cleaning the substrates adhere to the substrates, and the adhered sulfur-containing substances are removed by sputtering with argon. However, the technique disclosed in Patent Document 3 physically removes the sulfur-containing substances, which causes a problem of the removed sulfur-containing substances re-adhering to other locations within the plasma cleaning apparatus.

[0007] Therefore, when chalcogen-containing substances adhere to the inner surface of the reaction vessel, it is necessary to disassemble the passivation device and clean the reaction vessel. An object of the present disclosure is to provide a corrosion-resistant member that is unlikely to react with hydrogen chalcogenide even at high temperatures and is unlikely to produce chalcogen-containing substances.

[0008] In order to solve the above problems, one aspect of the present disclosure is as follows: [1] to [4]: ​​[1] A corrosion-resistant member provided in a passivation apparatus having a reaction vessel for performing passivation using hydrogen chalcogenide gas, and forming a portion of the reaction vessel that comes into contact with the hydrogen chalcogenide gas, the corrosion-resistant member having a sintered body containing at least one selected from aluminum oxide, aluminum nitride, zirconium oxide, zirconium nitride, silicon oxide, silicon nitride, and boron nitride, wherein the total proportion of aluminum oxide, aluminum nitride, zirconium oxide, zirconium nitride, silicon oxide, silicon nitride, and boron nitride in the sintered body exceeds 90 mass%.

[0009] [2] The corrosion-resistant member according to [1], wherein the boron nitride is boron nitride and the proportion of boron nitride in the sintered body is more than 90 mass %. [3] The corrosion-resistant member according to [1] or [2], wherein the arithmetic mean roughness Ra of the surface is 1 μm or less. [4] The corrosion-resistant member according to any one of [1] to [3], wherein the hydrogen chalcogenide is hydrogen sulfide.

[0010] The corrosion-resistant member according to the present disclosure is less likely to react with hydrogen chalcogenide even at high temperatures, and is less likely to produce chalcogen-containing substances.

[0011] FIG. 1 is a schematic diagram showing an example of an apparatus for evaluating the corrosion resistance of a corrosion-resistant member.

[0012] An embodiment of the present disclosure will be described below. Note that this embodiment shows an example of the present disclosure, and the present disclosure is not limited to this embodiment. Furthermore, various modifications or improvements can be made to this embodiment, and such modifications or improvements may also be included in the present disclosure.

[0013] The corrosion-resistant member according to this embodiment is provided in a passivation apparatus having a reaction vessel for passivating using hydrogen chalcogenide gas, and forms a portion of the reaction vessel that comes into contact with the hydrogen chalcogenide gas. The corrosion-resistant member according to this embodiment has a sintered body containing at least one selected from aluminum oxide, aluminum nitride, zirconium oxide, zirconium nitride, silicon oxide, silicon nitride, and boron nitride, and the total proportion of aluminum oxide, aluminum nitride, zirconium oxide, zirconium nitride, silicon oxide, silicon nitride, and boron nitride in the sintered body exceeds 90 mass%.

[0014] Since the corrosion-resistant member according to this embodiment has a sintered body having the above-described configuration, it is unlikely to react with hydrogen chalcogenide even at high temperatures, and chalcogen-containing substances are unlikely to be generated due to corrosion or decomposition. Therefore, if a portion of a reaction vessel that is provided in a passivation device and that performs passivation and that comes into contact with hydrogen chalcogenide gas is formed from the corrosion-resistant member according to this embodiment, chalcogen-containing substances generated by corrosion or decomposition are unlikely to adhere to the portion of the reaction vessel that comes into contact with hydrogen chalcogenide gas (e.g., the inner surface of the reaction vessel).

[0015] Therefore, when passivation of a substrate such as a wafer is performed using the passivation apparatus, chalcogen-containing substances are unlikely to adhere to the substrate, making it possible to manufacture semiconductors with excellent performance. Furthermore, because chalcogen-containing substances are unlikely to adhere to the portion of the reaction vessel in which passivation is performed that comes into contact with hydrogen chalcogenide gas, it is possible to remove the chalcogen-containing substances without disassembling and cleaning the passivation apparatus.

[0016] The corrosion-resistant member according to this embodiment is resistant to reaction with hydrogen chalcogenide even at high temperatures, and is resistant to the generation of chalcogen-containing substances due to corrosion or decomposition. However, the degree of resistance to the generation of chalcogen-containing substances is as follows: That is, when the corrosion-resistant member according to this embodiment is passivated using hydrogen chalcogenide (e.g., hydrogen sulfide) gas at 600°C for 6 hours and then the surface of the corrosion-resistant member is analyzed, the amount of chalcogen (e.g., sulfur) detected in the outermost layer of the corrosion-resistant member is 0.60 mass% or less. The method for detecting chalcogen is not particularly limited, but X-ray photoelectron spectroscopy (XPS) or energy dispersive X-ray spectroscopy (EDS) can be used.

[0017] The corrosion-resistant member according to this embodiment will be described in more detail below. [Sintered body] The sintered body contains at least one material selected from the group consisting of aluminum oxide, aluminum nitride, zirconium oxide, zirconium nitride, silicon oxide, silicon nitride, and boron nitride. Examples include alumina (Al2O3), aluminum nitride (AlN), mullite (3Al2O3.2SiO2), zirconium dioxide (ZrO2), zirconium nitride (ZrN), zircon (ZrSiO4), silicon oxide (SiO2), silicon nitride (Si3N4), sialon (Si3N4.Al2O3), and boron nitride (BN).

[0018] The total content of aluminum oxide, aluminum nitride, zirconium oxide, zirconium nitride, silicon oxide, silicon nitride, and boron nitride in the sintered body must exceed 90% by mass. Therefore, the sintered body may contain components other than the above components as long as their content in the sintered body is less than 10% by mass. For example, the sintered body may contain a sintering aid. Examples of sintering aids include sodium oxide (NaO), potassium oxide (KO), magnesium oxide (MgO), calcium oxide (CaO), barium oxide (BaO), yttrium oxide (YO), iron oxide (FeO), and titanium oxide (TiO).

[0019] The crystalline form of the components is not particularly limited as long as corrosion resistance is obtained, and examples thereof include single crystal, polycrystalline, microcrystalline, amorphous, etc. From the viewpoint of high corrosion resistance, amorphous is preferable if possible. The elemental composition of the components can be analyzed using, for example, X-ray fluorescence spectroscopy (XRF), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDS), glow discharge mass spectrometry (GD-MS), inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma atomic emission spectrometry (ICP-AES), and time-of-flight secondary ion mass spectrometry (TOF-SIMS).

[0020] [Passivation Apparatus] Of the reaction vessel provided in the passivation apparatus and performing passivation, the portion that comes into contact with hydrogen chalcogenide gas is formed of the corrosion-resistant member according to this embodiment. Only the portion of the reaction vessel that comes into contact with hydrogen chalcogenide gas may be formed of the corrosion-resistant member according to this embodiment, or the entire reaction vessel may be formed of the corrosion-resistant member according to this embodiment. Examples of the portion of the reaction vessel that comes into contact with hydrogen chalcogenide gas include the inner surface of the reaction vessel and its vicinity, i.e., the wall surrounding the space where passivation is performed.

[0021] The type of passivation device is not particularly limited, but specific examples include semiconductor manufacturing devices, etching devices, film formation devices, vapor deposition devices, ALD devices, CVD devices, PVD devices, plasma processing devices, chambers, reaction chambers (tanks), processing chambers (tanks), process chambers (tanks), reaction furnaces, tubular furnaces, furnace core tubes, tube furnaces, reduction furnaces, electric furnaces, firing furnaces, annealing furnaces, ceramic furnaces, ceramic tubes, etc.

[0022] The corrosion-resistant member according to this embodiment may be made entirely of the sintered body, or may be made by forming a coating of the sintered body on the surface of a substrate made of metal, ceramic, etc. The method for producing the corrosion-resistant member according to this embodiment is not particularly limited, and examples thereof include hot pressing, spark plasma sintering, reactive sintering, melting, thermal spraying, sol-gel method, chemical vapor deposition (CVD), and physical vapor deposition (PVD).

[0023] [Arithmetic mean roughness Ra] The arithmetic mean roughness Ra of the surface of the corrosion-resistant member according to this embodiment is preferably 1 μm or less. If the arithmetic mean roughness Ra of the surface is 1 μm or less, the surface area of ​​the corrosion-resistant member is small, so that hydrogen chalcogenide gas is less likely to be adsorbed onto the surface of the corrosion-resistant member. The arithmetic mean roughness Ra of the surface can be measured using a laser microscope.

[0024] [Hydrogen Chalcogenide] The type of hydrogen chalcogenide is not particularly limited, but examples include hydrogen sulfide (HS), hydrogen selenide (HSe), and hydrogen telluride (HTe). These hydrogen chalcogenides may be used alone or in combination of two or more.

[0025] The passivation gas used in passivation contains hydrogen chalcogenide gas. The concentration of hydrogen chalcogenide in the passivation gas is not particularly limited as long as it is sufficient for forming a passivation film, but is preferably 20% by volume or more, more preferably 50% by volume or more, and even more preferably 100% by volume. The passivation gas may contain gas components other than hydrogen chalcogenide, and the type of gas is not particularly limited, but examples include inert gases such as nitrogen gas (N), helium (He), and argon (Ar). The inert gas is also used as a cleaning gas for cleaning the inside of the passivation device system.

[0026] Next, an example of an apparatus for evaluating the corrosion resistance of a corrosion-resistant member according to this embodiment will be described with reference to Fig. 1. First, the configuration of the apparatus shown in Fig. 1 will be described. The apparatus shown in Fig. 1 includes a gas cylinder 1 filled with hydrogen chalcogenide gas, an inert gas cylinder 2 filled with an inert gas for diluting the hydrogen chalcogenide gas, a mass flow controller 3 for controlling the flow rate of the hydrogen chalcogenide gas, a mass flow controller 4 for controlling the flow rate of the inert gas, a reaction chamber 5 in which passivation of the corrosion-resistant member is performed, a heating device 6 for heating the gas and the corrosion-resistant member in the reaction chamber 5, a pressure gauge 7 for measuring the pressure in the reaction chamber 5, and a thermometer 8 for measuring the temperature in the reaction chamber 5.

[0027] Furthermore, valves 12 and 13 for adjusting the pressure inside the reaction chamber 5 are connected before and after the reaction chamber 5. Furthermore, the apparatus of Fig. 1 is equipped with a vacuum pump 9 for reducing the pressure inside the system of the apparatus, and a detoxification tank 10 and a detoxification liquid 11 for removing harmful substances from the passivation gas after passivation is completed and before the passivation gas is exhausted to the outside of the apparatus. These are connected to each other by piping as shown in Fig. 1.

[0028] Next, a method for evaluating the corrosion resistance of a corrosion-resistant member using the apparatus of FIG. 1 will be described. First, a member whose corrosion resistance is to be evaluated is placed in reaction chamber 5, and then the pressure inside the apparatus is reduced using vacuum pump 9. Next, hydrogen chalcogenide gas in gas cylinder 1 is sent to reaction chamber 5 by mass flow controller 3. Also, inert gas in inert gas cylinder 2 is sent to reaction chamber 5 by mass flow controller 4. At this time, the concentration of hydrogen chalcogenide gas in the passivation gas supplied into reaction chamber 5 can be arbitrarily controlled by mass flow controllers 3 and 4. For example, if only hydrogen chalcogenide gas and no inert gas are supplied into reaction chamber 5, a passivation gas with a 100% concentration of hydrogen chalcogenide gas can be supplied into reaction chamber 5.

[0029] The material forming the reaction chamber 5 is not particularly limited as long as it is resistant to hydrogen chalcogenide gas, but examples include aluminum with anodized surfaces. The structure of the reaction chamber 5 is not particularly limited, but it is preferable that it has a structure that allows pressure reduction to a predetermined level. The same is true for the piping connected to the reaction chamber 5, which is preferably formed from a material that is resistant to hydrogen chalcogenide gas and has a structure that can withstand the predetermined pressure.

[0030] In the passivation process, the temperature in the reaction chamber 5 is controlled as desired using a heating device 6. The temperature at which the corrosion-resistant member and the passivation gas are reacted in the passivation process is not particularly limited. However, considering the film formation temperature in the passivation process, it is preferable to obtain high in-plane uniformity in the treatment with the passivation gas when passivating the surface of the substrate. To this end, the temperature at which the corrosion-resistant member and the passivation gas are reacted in the passivation process is preferably 20°C or higher and 1500°C or lower, more preferably 50°C or higher and 1200°C or lower, even more preferably 100°C or higher and 1000°C or lower, and particularly preferably 100°C or higher and 900°C or lower.

[0031] The pressure inside the reaction chamber 5 during the passivation process can be arbitrarily controlled using the mass flow controllers 3 and 4 and the vacuum pump 9. The film formation pressure during the passivation process is not particularly limited, but is preferably 1 Pa or more and 1.0 MPa or less, more preferably 10 Pa or more and 0.9 MPa or less, and even more preferably 100 Pa or more and 0.8 MPa or less. That is, the corrosion-resistant member according to this embodiment is preferably provided in a passivation apparatus having a reaction vessel that performs passivation using hydrogen chalcogenide gas at a temperature of 20°C or more and 1500°C or less, and the temperature is more preferably 50°C or more and 1200°C or less, even more preferably 100°C or more and 1000°C or less, and particularly preferably 100°C or more and 900°C or less.

[0032] The passivation time in the passivation step is not particularly limited, but considering the efficiency of the semiconductor device manufacturing process, it is preferably within 120 minutes. The passivation time refers to the time from when a passivation gas is supplied into a passivation apparatus containing a substrate to when the passivation gas is exhausted using a vacuum pump or the like to complete the substrate surface treatment. After passivation is complete, the hydrogen chalcogenide gas is exhausted from the apparatus to the outside. However, if the exhaust gas contains harmful substances, the exhaust gas can be sent to a detoxification tank 10 and a detoxification liquid 11, where the harmful substances can be removed before being exhausted to the outside. The detoxification tank 10 is filled with a detoxification liquid 11, such as a potassium hydroxide aqueous solution, to remove harmful substances from the exhaust gas after passivation is complete.

[0033] The present disclosure will be described in more detail below with reference to examples and comparative examples. (Example 1) Passivation of a corrosion-resistant member was performed using an apparatus similar to that shown in FIG. 1. The following description is given. A boron nitride plate (15 mm long, 15 mm wide, 1 mm thick) was placed as a corrosion-resistant member in a reaction chamber (an alumina furnace tube manufactured by Heattec Co., Ltd., inner diameter 50 mm, length 600 mm) equipped with a pressure gauge and a thermometer. This plate was made of a boron nitride sintered body. That is, the sintered body contained boron nitride, and the proportion of the boron nitride in the sintered body was 100 mass%. The arithmetic mean roughness Ra of the surface of this plate is as shown in Table 1. In addition, the "proportion of components" in Table 1 refers to the "total proportion of aluminum oxide, aluminum nitride, zirconium oxide, zirconium nitride, silicon oxide, silicon nitride, and boron nitride in the sintered body."

[0034] The reaction chamber was heated using a tubular furnace until the thermometer reading reached 800°C. After reaching 800°C, the pressure inside the reaction chamber was reduced to 0.00 MPaA using a vacuum pump (DTC-22 manufactured by ULVAC KIKO Co., Ltd.). Once the pressure was reduced, the valve downstream of the reaction chamber was closed, and hydrogen sulfide gas (manufactured by Sumitomo Seika Chemicals Co., Ltd., purity 99.9% by volume or higher) with a flow rate adjusted to 500 mL / min using a mass flow controller (digital mass flow controller SEC-N100 manufactured by HORIBA STEC Co., Ltd.) was supplied into the reaction chamber until the pressure inside the reaction chamber reached 1.00 MPaA.

[0035] After hydrogen sulfide gas was introduced into the reaction chamber until the pressure reached 1.00 MPaA, the upstream valve of the reaction chamber was closed to seal the reaction chamber. The temperature inside the reaction chamber was then maintained at 800°C for 60 minutes, allowing the plate material to be passivated using hydrogen sulfide gas. After the retention time had elapsed, the downstream valve of the reaction chamber was opened, and the hydrogen sulfide gas in the reaction chamber was sent to the detoxification tank, where it was absorbed by the detoxification solution. After the hydrogen sulfide gas detoxification was complete, the system was cleaned by 50 purges using an inert gas (nitrogen gas). After the cleaning was complete, the reaction chamber was opened, the plate material was removed, and EDS analysis of the plate material's surface was performed to measure the sulfur concentration. The results are shown in Table 1.

[0036] The analytical device and analytical conditions used for the EDS analysis are as follows: Analytical device: JSM-IT200 manufactured by JEOL Ltd. WD: 10 mm Process time: T3 Acceleration voltage: 10 kV Probe current: 70 A Analysis range: 1.229 mm 2

[0037] (Example 2) Nitrogen gas and hydrogen sulfide gas were mixed to produce a mixed gas with a hydrogen sulfide concentration of 50% by volume, and passivation was performed using this mixed gas as the passivation gas. The passivation and analysis of plate materials using hydrogen sulfide gas were performed in the same manner as in Example 1, except that passivation was performed at a temperature of 600°C. The results are shown in Table 1. (Example 3) Passivation and analysis of plate materials using hydrogen sulfide gas were performed in the same manner as in Example 1, except that passivation was performed at a temperature of 600°C. The results are shown in Table 1.

[0038] (Example 4) Passivation and analysis of plate materials using hydrogen sulfide gas were carried out in the same manner as in Example 1, except that passivation was carried out for 360 minutes. The results are shown in Table 1. (Example 5) Passivation and analysis of plate materials using hydrogen sulfide gas were carried out in the same manner as in Example 1, except that passivation was carried out under a pressure of 1.50 MPaA. The results are shown in Table 1.

[0039] (Example 6) Passivation and analysis of plate materials using hydrogen sulfide gas were carried out in the same manner as in Example 1, except that passivation was carried out at a temperature of 900°C. The results are shown in Table 1. (Example 7) Passivation and analysis of plate materials using hydrogen sulfide gas were carried out in the same manner as in Example 1, except that passivation was carried out at a temperature of 400°C. The results are shown in Table 1. (Example 8) Passivation and analysis of plate materials using hydrogen sulfide gas were carried out in the same manner as in Example 1, except that passivation was carried out at a temperature of 100°C. The results are shown in Table 1. (Example 9) Passivation and analysis of plate materials using hydrogen sulfide gas were carried out in the same manner as in Example 1, except that passivation was carried out at a temperature of 20°C. The results are shown in Table 1.

[0040] Example 10: The plate was passivated and analyzed using hydrogen sulfide gas in the same manner as in Example 1, except that a quartz polishing plate (GE214 manufactured by Heattec Corporation, 15 mm long, 15 mm wide, and 1 mm thick) was used as the corrosion-resistant member. The results are shown in Table 1. The plate was made of a quartz sintered body. That is, the sintered body contained silicon dioxide, and the proportion of silicon dioxide in the sintered body was 100% by mass. Example 11: The plate was passivated and analyzed using hydrogen sulfide gas in the same manner as in Example 10, except that nitrogen gas and hydrogen sulfide gas were mixed to produce a mixed gas with a hydrogen sulfide concentration of 50% by volume, and this mixed gas was used as the passivation gas for passivation. The results are shown in Table 1.

[0041] Example 12: A zirconia plate (15 mm long, 15 mm wide, 1 mm thick) was used as the corrosion-resistant member. The plate was passivated using hydrogen sulfide gas and analyzed in the same manner as in Example 1. The results are shown in Table 1. The plate consisted of a sintered compact of a mixed powder consisting of 94.3 wt% zirconium dioxide (ZrO), 5.2 wt% yttria (YO), 0.3 wt% alumina, 0.1 wt% silicon dioxide, 0.1 wt% iron oxide (FeO), and 0.1 wt% sodium oxide (NaO). The sintered compact contained zirconium dioxide, alumina, and silicon dioxide, with the total proportion of zirconium dioxide, alumina, and silicon dioxide in the sintered compact being 94.7 wt%.

[0042] Example 13: Nitrogen gas and hydrogen sulfide gas were mixed to produce a mixed gas with a hydrogen sulfide concentration of 50% by volume, and passivation was performed using this mixed gas as the passivation gas. The passivation and analysis of plate materials using hydrogen sulfide gas were performed in the same manner as in Example 12. The results are shown in Table 1.

[0043] Example 14: A zircon plate (15 mm long, 15 mm wide, 1 mm thick) was used as the corrosion-resistant member. The plate was passivated using hydrogen sulfide gas and analyzed in the same manner as in Example 1. The results are shown in Table 1. The plate was made of a sintered compact of a mixed powder consisting of 79.0 wt% zircon (ZrSiO), 10.8 wt% silicon dioxide, 4.9 wt% alumina, 1.7 wt% barium oxide (BaO), 1.6 wt% calcium oxide (CaO), 1.3 wt% magnesium oxide (MgO), 0.3 wt% iron oxide (FeO), 0.2 wt% titanium dioxide (TiO), 0.2 wt% potassium oxide (KO), and 0.1 wt% sodium oxide. That is, the sintered body contains zircon, silicon dioxide, and alumina, and the total proportion of zircon, silicon dioxide, and alumina in the sintered body is 94.7 mass %.

[0044] Example 15: Nitrogen gas and hydrogen sulfide gas were mixed to produce a mixed gas with a hydrogen sulfide concentration of 50% by volume, and passivation was performed using this mixed gas as the passivation gas. The passivation and analysis of plate materials using hydrogen sulfide gas were performed in the same manner as in Example 14. The results are shown in Table 1.

[0045] Example 16: A mullite plate (15 mm long, 15 mm wide, 1 mm thick) was used as the corrosion-resistant member. The plate was passivated using hydrogen sulfide gas and analyzed in the same manner as in Example 1. The results are shown in Table 1. This plate consisted of a sintered compact of a mixed powder consisting of 54.3 wt% alumina, 40.7 wt% silicon dioxide, 3.3 wt% potassium oxide, 1.0 wt% sodium oxide, 0.2 wt% iron oxide (FeO), 0.2 wt% calcium oxide, and 0.1 wt% magnesium oxide. The sintered compact contained alumina and silicon dioxide, with the total proportion of alumina and silicon dioxide in the sintered compact being 95.0 wt%.

[0046] Example 17: Nitrogen gas and hydrogen sulfide gas were mixed to produce a mixed gas with a hydrogen sulfide concentration of 50% by volume, and passivation was performed using this mixed gas as the passivation gas. The passivation and analysis of plate materials using hydrogen sulfide gas were carried out in the same manner as in Example 16. The results are shown in Table 1.

[0047] Example 18: Passivation of the plate using hydrogen sulfide gas and analysis were carried out in the same manner as in Example 1, except that an alumina plate (15 mm long, 15 mm wide, 1 mm thick) was used as the corrosion-resistant member. The results are shown in Table 1. This plate was made of a sintered body of a mixed powder of 96.0 mass% alumina, 2.0 mass% silicon dioxide, 1.0 mass% calcium oxide, and 1.0 mass% magnesium oxide. That is, the sintered body contained alumina and silicon dioxide, with the total proportion of alumina and silicon dioxide in the sintered body being 98.0 mass%.

[0048] (Example 19) Passivation and analysis of plate materials using hydrogen sulfide gas were carried out in the same manner as in Example 18, except that passivation was carried out at a temperature of 900°C. The results are shown in Table 1. (Example 20) Passivation and analysis of plate materials using hydrogen sulfide gas were carried out in the same manner as in Example 18, except that passivation was carried out at a temperature of 400°C. The results are shown in Table 1. (Example 21) Passivation and analysis of plate materials using hydrogen sulfide gas were carried out in the same manner as in Example 18, except that passivation was carried out at a temperature of 100°C. The results are shown in Table 1. (Example 22) Passivation and analysis of plate materials using hydrogen sulfide gas were carried out in the same manner as in Example 18, except that passivation was carried out at a temperature of 20°C. The results are shown in Table 1.

[0049] (Example 23) Nitrogen gas and hydrogen sulfide gas were mixed to produce a mixed gas with a hydrogen sulfide concentration of 50% by volume, and passivation was performed using this mixed gas as the passivation gas. The passivation and analysis of plate materials using hydrogen sulfide gas were performed in the same manner as in Example 18, except that passivation was performed at a temperature of 100°C. The results are shown in Table 1. (Example 24) Passivation and analysis of plate materials using hydrogen sulfide gas were performed in the same manner as in Example 23, except that passivation was performed at a temperature of 100°C. The results are shown in Table 1.

[0050] Example 25: Passivation of the plate using hydrogen sulfide gas and analysis were carried out in the same manner as in Example 1, except that an aluminum nitride plate (15 mm long, 15 mm wide, 1 mm thick) was used as the corrosion-resistant member. The results are shown in Table 1. This plate was made of a sintered body of a mixed powder of 95.0 mass % aluminum nitride and 5.0 mass % yttria. That is, the sintered body contained aluminum nitride, and the proportion of aluminum nitride in the sintered body was 95.0 mass %.

[0051] Example 26: Nitrogen gas and hydrogen sulfide gas were mixed to produce a mixed gas with a hydrogen sulfide concentration of 50% by volume, and passivation was performed using this mixed gas as the passivation gas. The passivation and analysis of plate materials using hydrogen sulfide gas were performed in the same manner as in Example 25. The results are shown in Table 1.

[0052] Example 27: A zirconia plate (15 mm long, 15 mm wide, 1 mm thick) was used as the corrosion-resistant member. The plate was passivated using hydrogen sulfide gas and analyzed in the same manner as in Example 1. The results are shown in Table 1. This plate was made of a sintered compact of a mixed powder of 91.5% by mass of zirconium dioxide and 8.0% by mass of yttria. That is, the sintered compact contained zirconium dioxide, with the proportion of zirconium dioxide in the sintered compact being 91.5% by mass.

[0053] Comparative Example 1: A plate (15 mm long, 15 mm wide, 1 mm thick) made of quartz and alumina was used as the corrosion-resistant member. The plate was passivated using hydrogen sulfide gas and analyzed in the same manner as in Example 1. The results are shown in Table 1. This plate was made of a sintered compact of a mixed powder containing 48.7% by weight of silicon dioxide, 39.3% by weight of alumina, 10.0% by weight of magnesium oxide, 0.7% by weight of iron trioxide, 0.6% by weight of titanium oxide, 0.5% by weight of calcium oxide, 0.2% by weight of potassium oxide, and 0.1% by weight of sodium oxide. The sintered compact contained silicon dioxide and alumina, with the total proportion of silicon dioxide and alumina in the sintered compact being 88.0% by weight.

[0054] Comparative Example 2: A plate (15 mm long, 15 mm wide, 1 mm thick) made of yttria was used as the corrosion-resistant member. The plate was passivated using hydrogen sulfide gas and analyzed in the same manner as in Example 1. The results are shown in Table 1. This plate was made of a sintered body of yttria. Since this plate did not contain aluminum oxide, aluminum nitride, zirconium oxide, zirconium nitride, silicon oxide, silicon nitride, or boron nitride, the total proportion of these components in the sintered body was 0% by mass.

[0055] (Comparative Example 3) Nitrogen gas and hydrogen sulfide gas were mixed to produce a mixed gas with a hydrogen sulfide concentration of 50% by volume, and passivation was performed using this mixed gas as the passivation gas, except that passivation was performed using hydrogen sulfide gas and analysis of the plate material was performed in the same manner as in Comparative Example 2. The results are shown in Table 1.

[0056] (Comparative Example 4) Passivation and analysis of plate material using hydrogen sulfide gas were carried out in the same manner as in Comparative Example 2, except that passivation was carried out at a temperature of 600°C. The results are shown in Table 1. (Comparative Example 5) Passivation and analysis of plate material using hydrogen sulfide gas were carried out in the same manner as in Comparative Example 2, except that passivation was carried out at a temperature of 400°C. The results are shown in Table 1. (Comparative Example 6) Passivation and analysis of plate material using hydrogen sulfide gas were carried out in the same manner as in Comparative Example 2, except that passivation was carried out for 360 minutes. The results are shown in Table 1.

[0057] Comparative Example 7: Passivation and analysis of the plate using hydrogen sulfide gas were carried out in the same manner as in Example 1, except that an aluminum plate (length 15 mm, width 15 mm, thickness 1 mm) was used as the corrosion-resistant member. The results are shown in Table 1. Note that this plate is an aluminum metal plate. In other words, this plate does not contain aluminum oxide, aluminum nitride, zirconium oxide, zirconium nitride, silicon oxide, silicon nitride, or boron nitride, and therefore the total proportion of these components is 0% by mass.

[0058] Comparative Example 8: A nickel plate (15 mm long, 15 mm wide, 1 mm thick) was used as the corrosion-resistant member. The plate was passivated using hydrogen sulfide gas and analyzed in the same manner as in Example 1. The results are shown in Table 1. This plate was a nickel metal plate. Since this plate did not contain aluminum oxide, aluminum nitride, zirconium oxide, zirconium nitride, silicon oxide, silicon nitride, or boron nitride, the total proportion of these components was 0% by mass.

[0059] (Comparative Example 9) Passivation and analysis of plate material using hydrogen sulfide gas were carried out in the same manner as in Comparative Example 8, except that passivation was carried out at a temperature of 100°C. The results are shown in Table 1. (Comparative Example 10) Passivation and analysis of plate material using hydrogen sulfide gas were carried out in the same manner as in Comparative Example 8, except that passivation was carried out at a temperature of 50°C. The results are shown in Table 1.

[0060] Comparative Example 11: A chromium plate (15 mm long, 15 mm wide, 1 mm thick) was used as the corrosion-resistant member. The plate was passivated using hydrogen sulfide gas and analyzed in the same manner as in Example 1. The results are shown in Table 1. This plate was a chromium metal plate. Since this plate did not contain aluminum oxide, aluminum nitride, zirconium oxide, zirconium nitride, silicon oxide, silicon nitride, or boron nitride, the total proportion of these components was 0% by mass.

[0061]

[0062] As can be seen from the results of Examples 1 to 27, when the sintered body contained at least one selected from aluminum oxide, zirconium oxide, silicon oxide, aluminum nitride, and boron nitride, and the total proportion of these components in the sintered body exceeded 90% by mass, the sulfur concentration on the surface of the plate after passivation was 0.60% by mass or less. In other words, the corrosion-resistant members used in Examples 1 to 27 hardly reacted with hydrogen chalcogenide even in high-temperature environments, and the amount of chalcogen-containing substances produced by corrosion or decomposition was extremely small. Therefore, the corrosion-resistant members used in Examples 1 to 27 are suitable as components for forming the reaction vessel of a passivation device.

[0063] In contrast, in Comparative Examples 1 to 11, the plate materials used did not contain a sintered body containing at least one selected from aluminum oxide, aluminum nitride, zirconium oxide, zirconium nitride, silicon oxide, silicon nitride, and boron nitride, or even if they did contain a sintered body, the total proportion of the above components was 90 mass% or less, so sulfides were generated by reaction due to passivation, and the sulfur concentration on the surface of the plate material after passivation became a large value. Therefore, the plate materials used in Comparative Examples 1 to 11 are unsuitable as components for forming the reaction vessel of the passivation device.

[0064] 1... Gas cylinder 2... Inert gas cylinder 3... Mass flow controller 4... Mass flow controller 5... Reaction chamber 6... Heating device 9... Vacuum pump

Claims

1. A corrosion-resistant member provided in a passivation device having a reaction vessel in which passivation is performed using hydrogen chalcogenide gas, forming a portion of the reaction vessel that comes into contact with the hydrogen chalcogenide gas, the corrosion-resistant member having a sintered body containing at least one selected from aluminum oxide, aluminum nitride, zirconium oxide, zirconium nitride, silicon oxide, silicon nitride, and boron nitride, wherein the total proportion of aluminum oxide, aluminum nitride, zirconium oxide, zirconium nitride, silicon oxide, silicon nitride, and boron nitride in the sintered body exceeds 90 mass%.

2. The corrosion-resistant member according to claim 1, wherein the nitride of boron is boron nitride, and the proportion of boron nitride in the sintered body is more than 90 mass %.

3. A corrosion-resistant member according to claim 1 or 2, wherein the arithmetic mean roughness Ra of the surface is 1 μm or less.

4. A corrosion-resistant member according to claim 1 or 2, wherein the hydrogen chalcogenide is hydrogen sulfide.

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