Method for removing deposits and method for forming film

Abstract

The present invention provides: a method for removing an adhering material, said method enabling removal of an adhering material, which contains selenium and adheres to the inner surface of a chamber or the inner surface of a pipe that is connected to the chamber, without dismantling the chamber; and a film forming method. According to the present invention, an adhering material, which contains selenium and adheres to at least either the inner surface of a chamber (10) or the inner surface of a discharge pipe (15) that is connected to the chamber (10), is removed by being reacted with a cleaning gas that contains a fluorine-containing compound gas.

Description

[Technical field]

[0001] The present invention relates to a method for removing deposits and a method for forming a film. [Background technology]

[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 having higher mobility than silicon materials, they can be difficult to form into films and can have high defect densities at the interfaces between materials.

[0003] 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 such as germanium or molybdenum using hydrogen selenide (H2Se) gas (see, for example, Patent Document 1).In addition, as a method for forming a metal chalcogenide film, a method has been proposed in which a molybdenum oxide layer and a tungsten oxide layer are treated with radicalized hydrogen selenide gas to form a molybdenum selenide layer and a tungsten selenide layer (see, for example, Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 207789, 2016 [Patent Document 2] Japan Patent Publication No. 61743, 2017 [Patent Document 3] Japan Patent Publication No. 66450, 2011 Summary of the Invention [Problem to be solved by the invention]

[0005] In the above-described method for reducing the defect density at the interface between materials, the reaction is carried out at high temperatures, and therefore, deposits containing selenium produced by decomposition of hydrogen selenide may adhere to the inner surface of the chamber in which the reaction is carried out or to the inner surface of a pipe disposed downstream of the chamber. If a substrate such as a wafer is introduced into the chamber with selenium-containing deposits on the inner surface of the chamber or the inner surface of the pipe disposed downstream of the chamber, there is a risk that selenium particles will adhere to the substrate such as the wafer when the chamber is evacuated and the atmosphere is replaced with an inert gas. If selenium particles adhere to the substrate, there is a risk that the performance of the manufactured semiconductor structure will be degraded.

[0006] For example, Patent Document 3 discloses a technique for etching a chalcogen compound semiconductor film containing selenium using a plasma etching device. In this technique, selenium derived from the etching product adheres to the inner surface of the chamber, and the adhered selenium is removed by plasma cleaning using a cleaning gas containing boron trichloride (BCl3) and chlorine (Cl2).

[0007] In the technology disclosed in Patent Document 3, selenium is removed by reacting it with chlorine, but the reaction product, selenium chloride, is in a solid state depending on the oxidation number of selenium, and therefore there is a problem that it may redeposit in another location in the plasma etching device or on the piping arranged downstream of the plasma etching device. Therefore, when deposits containing selenium chloride are attached to the inner surface of the chamber or the inner surface of the piping arranged downstream of the chamber, it is necessary to disassemble the chamber and clean it. An object of the present invention is to provide a method for removing selenium-containing deposits that are attached to the inner surface of a chamber or the inner surface of a pipe connected to the chamber, and a method for forming a film that can remove the deposits without dismantling the chamber. [Means for solving the problem]

[0008] In order to solve the above problems, one aspect of the present invention is as follows [1] to [6]. [1] A method for removing selenium-containing deposits adhering to at least one of the inner surface of a chamber and the inner surface of a pipe connected to the chamber by reacting the deposits with a cleaning gas containing a fluorine-containing compound gas.

[0009] [2] The method for removing adhesion according to [1], wherein the cleaning gas is brought into contact with the adhesion under conditions of a temperature of 20° C. or higher and 800° C. or lower and a pressure of 20 Pa or higher and 101 kPa or lower. [3] The method for removing adhesions according to [1] or [2], wherein the fluorine-containing compound gas is at least one selected from the group consisting of fluorine gas, nitrogen trifluoride gas, and fluorinated hydrocarbon gas, and the fluorinated hydrocarbon gas is at least one gas selected from the group consisting of compounds represented by the following formulas (1), (2), (3), and (4): CH 4-m F m (1) C2H 6-n F n (2) C3H 8-q F q (3) C4H 10-r F r (4) Here, m in the above formula (1) is an integer of 1 or more and 4 or less, n in the above formula (2) is an integer of 1 or more and 6 or less, q in the above formula (3) is an integer of 1 or more and 8 or less, and r in the above formula (4) is an integer of 1 or more and 10 or less.

[0010] [4] The method for removing adhesions according to [1] or [2], wherein the fluorine-containing compound gas is fluorine gas. [5] a passivation process in which a passivation gas containing a selenium-containing compound gas is supplied to a chamber containing a substrate, and the substrate is reacted with the passivation gas to form a passivation film on a surface of the substrate; a deposit removing step of removing deposits containing selenium that are attached to at least one of the inner surface of the chamber and the inner surface of a pipe connected to the chamber after the passivation step is performed; Equipped with The film forming method, wherein the deposit removing step is carried out by the deposit removing method according to any one of [1] to [4]. [6] The film forming method according to [5], wherein the selenium-containing compound gas is hydrogen selenide gas. Effect of the Invention

[0011] According to the present invention, it is possible to remove selenium-containing deposits adhering to the inner surface of a chamber or the inner surface of a pipe connected to the chamber without dismantling the chamber. [Brief description of the drawings]

[0012] [Figure 1] 1 is a schematic diagram of a film forming apparatus for explaining an embodiment of a film forming method according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] An embodiment of the present invention will be described below. Note that this embodiment is merely an example of the present invention, and the present invention is not limited to this embodiment. In addition, various modifications and improvements can be made to this embodiment, and such modifications and improvements can also be included in the present invention.

[0014] First Embodiment The first embodiment of the present invention is an embodiment of a method for removing deposits, which is a method for removing deposits containing selenium (hereinafter, sometimes simply referred to as "deposits") that are attached to at least one of the inner surface of a chamber and the inner surface of a pipe connected to the chamber, by reacting the deposits with a cleaning gas containing a fluorine-containing compound gas. Note that the fluorine-containing compound gas and the cleaning gas do not contain selenium atoms.

[0015] When a reaction using selenium is carried out in a chamber, selenium-containing deposits may adhere to the inner surface of the chamber or the inner surface of piping connected to the chamber (for example, a cleaning gas supply piping connected to the upstream side of the chamber or an exhaust piping connected to the downstream side of the chamber). If the next reaction is carried out with the deposits still attached, the reaction may be adversely affected, so it is preferable to remove the deposits before carrying out the next reaction.

[0016] The method for removing deposits according to the first embodiment removes deposits by bringing a cleaning gas into contact with the deposits and reacting selenium in the deposits with a fluorine-containing compound gas in the cleaning gas to generate a selenium fluoride gas such as selenium hexafluoride, so that deposits adhering to the inner surface of the chamber or the inner surface of the pipes connected to the chamber can be removed without dismantling the chamber, and therefore the deposits can be easily removed.

[0017] The contact between the cleaning gas and the deposit is preferably performed under a temperature condition of 20° C. to 800° C., more preferably 40° C. to 600° C. If the temperature is 800° C. or less, the fluorine-containing compound gas in the cleaning gas and the generated selenium fluoride gas such as selenium hexafluoride are unlikely to corrode metal materials such as stainless steel forming the chamber and piping, and in addition, the reverse reaction in which the selenium fluoride gas such as selenium hexafluoride generated by the reaction between the selenium in the deposit and the fluorine-containing compound gas in the cleaning gas returns to selenium is unlikely to occur. On the other hand, if the temperature is 20° C. or more, the reaction between the selenium in the deposit and the fluorine-containing compound gas in the cleaning gas is likely to proceed.

[0018] In addition, the contact between the cleaning gas and the deposit is preferably performed under conditions of an absolute pressure of 20 Pa to 101 kPa, and more preferably under conditions of a pressure of 60 Pa to 90 kPa. If the pressure is 101 kPa or less, malfunctions are unlikely to occur in the chamber or piping. For example, if the chamber is a reaction vessel of a film forming device that reacts a substrate with a passivation gas to form a passivation film on the surface of the substrate, the pressure condition is preferably 101 kPa or less, since it is assumed that the chamber will be used in a reduced pressure environment. On the other hand, if the pressure is 20 Pa or more, the reaction between selenium in the deposit and the fluorine-containing compound gas in the cleaning gas is likely to proceed.

[0019] The fluorine-containing compound gas is a gas of a compound having a fluorine atom, and furthermore, does not have a selenium atom, and examples thereof include fluorine gas (F2), nitrogen trifluoride gas (NF3), and fluorinated hydrocarbon gas. The fluorinated hydrocarbon gas includes at least one gas selected from the compounds represented by the following formulas (1), (2), (3), and (4). CH 4-m F m (1) C2H 6-n F n (2) C3H 8-q F q (3) C4H 10-r F r (4) Here, m in the above formula (1) is an integer of 1 or more and 4 or less, n in the above formula (2) is an integer of 1 or more and 6 or less, q in the above formula (3) is an integer of 1 or more and 8 or less, and r in the above formula (4) is an integer of 1 or more and 10 or less.

[0020] Examples of the compound represented by the above formula (1) include tetrafluoromethane (CF4), trifluoromethane (CHF3), difluoromethane (CH2F2), and fluoromethane (CH3F). Examples of the compound represented by (2) above include hexafluoroethane (C2F6), pentafluoroethane (C2HF5), tetrafluoroethane (C2H2F4), trifluoroethane (C2H3F3), difluoroethane (C2H4F2), and fluoroethane (C2H5F).

[0021] Examples of the compound represented by (3) above include octafluoropropane (C3F8), heptafluoropropane (C3HF7), hexafluoropropane (C3H2F6), pentafluoropropane (C3H3F5), tetrafluoropropane (C3H4F4), trifluoropropane (C3H5F3), difluoropropane (C3H6F2), and fluoropropane (C3H7F).

[0022] An example of the compound represented by (4) above is decafluorobutane (CF 10 ), nonafluorobutane (C4HF9), octafluorobutane (C4H2F8), heptafluorobutane (C4H3F7), hexafluorobutane (C4H4F6), pentafluorobutane (C4H5F5), tetrafluorobutane (C4H6F4), trifluorobutane (C4H7F3), difluorobutane (C4H8F2), and fluorobutane (C4H9F).

[0023] In addition, the compounds are not limited to the above compounds as long as they are represented by the above formulas (1), (2), (3), and (4), and may include isomers. Among these fluorine-containing compound gases, fluorine gas, nitrogen trifluoride gas, and tetrafluoromethane are preferred, with fluorine gas being more preferred.

[0024] Fluorine gas reacts with selenium even at room temperature under a pressure of 101 kPa, but in order to increase the reaction efficiency, when the cleaning gas contains fluorine gas, it is preferable to bring the cleaning gas into contact with selenium (adherent matter) at a temperature of 50° C. to 800° C. When the cleaning gas contains fluorine gas, it is preferable to remove the adhering matter while heating the inside of the chamber and piping in order to efficiently remove the adhering matter.

[0025] The content ratio of the fluorine-containing compound gas in the cleaning gas is not particularly limited as long as it is an amount sufficient to remove selenium (adherent matter), but is preferably 5% by volume or more, more preferably 20% by volume or more, even more preferably 90% by volume or more, and particularly preferably 100% by volume. The components other than the fluorine-containing compound gas contained in the cleaning gas are not particularly limited as long as they are gases of compounds that do not have selenium atoms, but examples thereof include inert gases such as nitrogen gas and argon gas.

[0026] The chamber is not particularly limited as long as it is made of a material resistant to hydrogen selenide, but it is preferable that it has a structure that allows pressure reduction to a predetermined pressure, and examples of materials include aluminum with an anodized surface. The piping connected to the chamber is also not particularly limited as long as it is made of a material resistant to hydrogen selenide, but it is preferable that it has a structure that can withstand a predetermined pressure. For example, the deposit removal method according to the first embodiment can be suitably applied to a chamber provided as a reaction vessel in a semiconductor film forming apparatus and to the piping connected to the chamber.

[0027] Second Embodiment The second embodiment of the present invention is an embodiment of a film forming method, which includes a passivation step of supplying a passivation gas containing a selenium-containing compound gas to a chamber containing a substrate and reacting the substrate with the passivation gas to form a passivation film on the surface of the substrate, and an attachment removal step of removing selenium-containing attachments attached to at least one of the inner surface of the chamber and the inner surface of a pipe connected to the chamber after the passivation step is performed. This attachment removal step is performed by the attachment removal method of the first embodiment.

[0028] In a passivation process in which a passivation film is formed on the surface of a substrate using a passivation gas, selenium-containing deposits may adhere to the inner surface of the chamber or the inner surface of piping connected to the chamber (e.g., a supply pipe for passivation gas or cleaning gas connected to the upstream side of the chamber, or an exhaust pipe connected to the downstream side of the chamber).

[0029] If a substrate is introduced into the chamber with deposits adhering to the inner surface of the chamber or the inner surface of the piping, selenium particles may adhere to the substrate when the chamber is evacuated and replaced with an inert gas. If selenium particles adhere to the substrate, the performance of the manufactured semiconductor structure may be degraded. Furthermore, if the next passivation step is performed with selenium particles still adhering to the substrate, problems such as a decrease in the film formation speed and film quality of the passivation film may occur. Therefore, it is preferable to remove the deposits before performing the next passivation step.

[0030] In the film forming method according to the second embodiment, the deposits are removed by contacting the cleaning gas with the deposits and reacting the selenium in the deposits with the fluorine-containing compound gas in the cleaning gas to generate selenium fluoride gas such as selenium hexafluoride, so that the deposits adhering to the inner surface of the chamber or the inner surface of the pipe connected to the chamber can be removed without dismantling the chamber. Therefore, the deposits can be easily removed. Furthermore, with the film forming method according to the second embodiment, the removal of the deposits can suppress the adhesion of selenium particles to the substrate, so that a semiconductor structure with excellent performance can be manufactured.

[0031] In the film forming method according to the second embodiment, the attachment removal step does not necessarily have to be performed every time the passivation step is performed, and the attachment removal step may be performed after the passivation step is performed several times. By reducing the number of times the attachment removal step is performed relative to the number of times the passivation step is performed, the utilization efficiency of the film forming apparatus can be improved.

[0032] The type of passivation gas containing a selenium-containing compound gas is not particularly limited as long as it is a gas of a compound containing selenium, but hydrogen selenide gas is preferred because of its good passivation performance. The content ratio of the selenium-containing compound gas in the passivation gas is not particularly limited as long as it is sufficient for forming a passivation film, but is preferably 1% by volume or more, more preferably 2% by volume or more, even more preferably 10% by volume or more, and particularly preferably 100% by volume. The components other than the selenium-containing compound gas contained in the passivation gas are not particularly limited, but examples thereof include inert gases such as nitrogen gas and argon gas.

[0033] The type of material forming the substrate is not particularly limited as long as it is a semiconductor material, and examples thereof include materials containing elements such as silicon, germanium, III-V group compounds, molybdenum, and tungsten. As silicon, silicon used in the formation of semiconductor elements is preferable, and examples thereof include amorphous silicon, polysilicon, and single crystal silicon. As germanium, III-V group compounds, molybdenum, and tungsten, those used in the formation of semiconductor elements are also preferable.

[0034] The pressure in the chamber when forming the passivation film in the passivation process is not particularly limited, but is preferably 1 Pa or more and 101 kPa or less, more preferably 10 Pa or more and 90 kPa or less, and even more preferably 100 Pa or more and 80 kPa or less.

[0035] The temperature of the substrate when reacting with the passivation gas in the passivation process is not particularly limited, but in order to obtain high in-plane uniformity in the treatment of the substrate surface with the passivation gas, the temperature is preferably 20°C or higher and 1500°C or lower, more preferably 50°C or higher and 1200°C or lower, and even more preferably 100°C or higher and 1000°C or lower.

[0036] In the passivation step, the length of the passivation time is not particularly limited, but considering the efficiency of the semiconductor device manufacturing process, it is preferable that it is within 120 minutes. Note that the passivation time refers to the time from when the passivation gas is supplied to the chamber containing the substrate to when the passivation gas in the chamber is exhausted by a vacuum pump or the like to finish the treatment of the substrate surface with the passivation gas.

[0037] The film formation method according to the second embodiment can be suitably applied to a semiconductor film formation apparatus that forms a passivation film on the surface of a substrate. The structure of this film formation apparatus is not particularly limited, and the positional relationship between the substrate accommodated in a chamber, which is a reaction vessel, and the pipes connected to the chamber is also not particularly limited. EXAMPLES

[0038] The present invention will be described in more detail below with reference to examples and comparative examples. Example 1 Using the film forming apparatus 1 shown in Fig. 1, a passivation step of forming a passivation film on the surface of a substrate and an adhesion removal step of removing adhesions containing selenium were repeatedly performed. The film forming apparatus 1 has a chamber 10 in which the passivation step and the adhesion removal step are performed, and a temperature adjustment device (not shown) that adjusts the temperature inside the chamber 10. Inside the chamber 10, a stage 11 that supports a sample 20 is provided. The sample 20 used was a silicon substrate having a silicon oxide film with a thickness of 150 nm formed thereon, and a molybdenum film with a thickness of 80 nm further formed thereon.

[0039] Connected to the chamber 10 on its upstream side via valves 32, 33, and 34 are a passivation gas supply pipe 12 for supplying a passivation gas containing a selenium-containing compound gas to the chamber 10, a cleaning gas supply pipe 13 for supplying a cleaning gas containing a fluorine-containing compound gas to the chamber 10, and an inert gas supply pipe 14 for supplying an inert gas to the chamber 10.

[0040] In addition, an exhaust pipe 15 for discharging gas inside the chamber 10 to the outside is connected to the downstream side of the chamber 10, and a vacuum pump 38 is connected to the downstream side of the exhaust pipe 15 via a valve 35. The pressure inside the chamber 10 is controlled by a pressure controller 37 that controls the valve 35.

[0041] Using such a film forming apparatus 1, a passivation process was first performed. The sample 20 was placed on the stage 11, and the pressure in the chamber 10 was reduced to less than 10 Pa, and then the temperature in the chamber 10 was raised to 800° C. Thereafter, the valve 32 was opened, and hydrogen selenide gas was supplied as a passivation gas from the passivation gas supply pipe 12 into the chamber 10 at a pressure of 101 kPa. The flow rate of the passivation gas at this time was 100 sccm, and the pressure in the chamber 10 when the passivation film was formed on the surface of the sample 20 was 67 kPa. Note that sccm represents the flow rate (mL / min) at 0° C. and 101.3 kPa.

[0042] The introduction of the passivation gas was continued for 30 minutes, and the surface of the sample 20 was selenized under conditions of a temperature of 800° C. and a pressure of 67 kPa to form a passivation film, after which the introduction of the passivation gas was stopped. Then, the inside of the chamber 10 was evacuated by the vacuum pump 38, and the inside of the chamber 10 was replaced with the inert gas by supplying the inert gas into the chamber 10 from the inert gas supply pipe 14. Thereafter, the temperature in the chamber 10 was lowered to room temperature, and the sample 20 on which the passivation film had been formed was taken out of the chamber 10.

[0043] Next, an adhesion removal step was performed using the film forming apparatus 1. After the pressure in the chamber 10 from which the sample 20 was removed was reduced to less than 10 Pa, the temperature in the chamber 10 was raised to 500° C. Thereafter, the valve 33 was opened, and a mixture of fluorine gas and nitrogen gas (the concentration of the fluorine gas was 20 volume % and the concentration of the nitrogen gas was 80 volume %) was supplied as a cleaning gas from the cleaning gas supply pipe 13 to the inside of the chamber 10 and the exhaust pipe 15. The flow rate of the cleaning gas at this time was 100 sccm, and the pressure in the chamber 10 when removing the adhesion was 67 kPa.

[0044] The cleaning gas was introduced for 5 minutes, and the deposits were removed by reacting them with the fluorine gas under conditions of a temperature of 500° C. and a pressure of 67 kPa, after which the introduction of the cleaning gas was stopped. Then, the inside of the chamber 10 was evacuated with the vacuum pump 38, and the inert gas was supplied into the chamber 10 from the inert gas supply pipe 14 to replace the inside of the chamber 10 with the inert gas.

[0045] After the attachment removal process was completed, the passivation process was performed in the same manner as described above, and a passivation film was formed on a new sample 20. Then, the attachment removal process was performed in the same manner as described above. By repeating this operation, a total of 100 samples 20 with a passivation film formed thereon were manufactured.

[0046] Example 2 Except for the fact that the temperature in the chamber 10 in the deposit removing step was set to 350° C. and the pressure was set to 100 Pa, 100 samples 20 each having a passivation film formed thereon were manufactured in the same manner as in Example 1. Example 3 100 samples 20 each having a passivation film formed thereon were manufactured in the same manner as in Example 1, except that the temperature inside the chamber 10 in the deposit removal step was set to 20°C.

[0047] Example 4 100 samples 20 each having a passivation film formed thereon were manufactured in the same manner as in Example 1, except that the temperature inside the chamber 10 in the deposit removal step was set to 800°C. Example 5 Except for the point that the pressure inside the chamber 10 in the deposit removing step was set to 20 Pa, 100 samples 20 each having a passivation film formed thereon were manufactured in the same manner as in Example 1.

[0048] Example 6 100 samples 20 each having a passivation film formed thereon were manufactured in the same manner as in Example 1, except that the pressure inside the chamber 10 in the deposit removal step was set to 101 kPa. Example 7 One hundred samples 20 having a passivation film formed thereon were manufactured in the same manner as in Example 1, except that the cleaning gas supplied from the cleaning gas supply pipe 13 in the adhesion removal process was nitrogen trifluoride gas (not a mixed gas with nitrogen gas, but 100 volume % nitrogen trifluoride gas).

[0049] Example 8 One hundred samples 20 having a passivation film formed thereon were manufactured in the same manner as in Example 1, except that the cleaning gas supplied from the cleaning gas supply pipe 13 in the adhesion removal process was tetrafluoromethane gas (100 volume% tetrafluoromethane gas, not a mixed gas with nitrogen gas).

[0050] Comparative Example 1 100 pieces of Sample 20 having a passivation film formed thereon were manufactured in the same manner as in Example 1, except that the deposit removal step was not performed and only the passivation step was repeatedly performed. For the samples 20 of Examples 1 to 8 and Comparative Example 1, the number of selenium particles adhering to the surface of the sample 20 was measured every time the passivation process was completed for the first to 100th samples 20. The particle number was measured using a wafer inspection device SurfScan (registered trademark) 6240 manufactured by KLA-Tencor Corporation. The measurement results are shown in Table 1.

[0051] [Table 1]

[0052] As can be seen from Table 1, in Comparative Example 1 in which only the passivation step was repeated without performing the adhesion removal step, the number of particles adhering to the sample 20 increased as the number of passivation steps performed increased, i.e., as the number of samples 20 on which a passivation film was formed increased, and the number of particles adhering to the sample 20 increased to 2000 particles / m at the 30th step. 2 Above 11,000 pieces / m for the 100th test. 2 That was all.

[0053] In contrast, in Examples 1 to 8 in which the deposit removal process was carried out after the passivation process, the number of particles adhering to the sample 20 was small, and in Example 1, the number was 100 particles / m even after the 100th passivation process. 2 In Example 2, the density was about 300 particles / m 2 In other examples, the number is about 1000 / m 2 The results were as follows. In this way, it was shown that by carrying out the deposit removal process, it is possible to repeatedly carry out the passivation process while keeping the number of adhering particles low, without having to disassemble and clean the chamber. [Explanation of symbols]

[0054] 1...Film deposition equipment 10. Chamber 11 Stage 12 Passivation gas supply pipe 13 Cleaning gas supply piping 14 Inert gas supply piping 15...Exhaust piping 20. Sample

Claims

1. removing selenium-containing deposits adhering to at least one of an inner surface of the chamber and an inner surface of a pipe connected to the chamber by reacting the deposits with a cleaning gas containing a fluorine-containing compound gas; the cleaning gas contains the fluorine-containing compound gas and an inert gas, and the content of the inert gas in the cleaning gas is 80% by volume or more; The cleaning gas is brought into contact with the deposit under conditions of a temperature of 20° C. or more and 800° C. or less and a pressure of 20 Pa or more and 101 kPa or less, The method for removing adhesion, wherein the fluorine-containing compound gas is at least one selected from the group consisting of fluorine gas, nitrogen trifluoride gas, and fluorinated hydrocarbon gas, and the fluorinated hydrocarbon gas is at least one gas selected from the group consisting of compounds represented by the following formulas (1), (2), (3), and (4): CH 4-m F m ... (1) C2H6-nFn...(2) C3H8-qFq...(3) C 4 H 10-r F r ... (4) Here, m in the above formula (1) is an integer of 1 or more and 4 or less, n in the above formula (2) is an integer of 1 or more and 6 or less, q in the above formula (3) is an integer of 1 or more and 8 or less, and r in the above formula (4) is an integer of 1 or more and 10 or less.

2. 2. The method for removing deposits according to claim 1, wherein the fluorine-containing compound gas is fluorine gas.

3. a passivation step of supplying a passivation gas containing a selenium-containing compound gas to a chamber containing a substrate and reacting the substrate with the passivation gas to form a passivation film on a surface of the substrate; a deposit removing step of removing deposits containing selenium that are attached to at least one of the inner surface of the chamber and the inner surface of a pipe connected to the chamber after the passivation step is performed; Equipped with A film forming method, wherein the deposit removing step is carried out by the deposit removing method according to claim 1 or 2.

4. 4. The film forming method according to claim 3, wherein the selenium-containing compound gas is hydrogen selenide gas.

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