TWI406111B - Method for removing resist and device - Google Patents

Abstract

To remove resist in a substrate without worrying about deformation because of thermal expansion near room temperature. Unsaturated hydrocarbon gas and ozone gas are supplied to a chamber 2 storing a substrate 10 supplied for removing resist 101 at room temperature under pressure lower than atmospheric pressure. The ozone gas is supplied from an ozone generator 4. The ozone generator 4 liquefies and separates only ozone based on a difference in vapor pressure from gas containing ozone and then vaporizes it again to obtain ultra-high concentration ozone gas. The chamber 2 may have a mixing chamber and a treatment chamber. The mixing chamber and the treatment chamber comprise a partition for dividing the chamber 2 into two chambers, namely upper and lower chambers. The unsaturated hydrocarbon gas and ozone gas are supplied into the mixing chamber. The mixed gas of the unsaturated hydrocarbon gas and ozone in the mixing chamber is transferred to the treatment chamber storing the substrate 10. The partition has a shower head for transferring gas in the mixing chamber into the treatment chamber. In the shower head, a plurality of holes are formed in the partition.

Description

Receptor removal method and device thereof

The present invention relates to a technique for removing a resist formed on a surface of a substrate during a manufacturing process of a semiconductor element, particularly a high-dose ion implantation resist.

Techniques for removing high-dose ion implantation resists on a substrate are disclosed, for example, in the following patent documents.

The plasma processing method and apparatus of Patent Document 1 use a spiral wave plasma treatment having a substrate bias application means and a substrate heating means, and a plasma treatment is applied to the substrate. Specifically, the substrate is removed by plasma treatment of the ion mode body according to the high ion current of the spiral wave plasma and plasma treatment of the radical mode body according to the non-resonant inductively coupled plasma. Resistive mask.

The plasma processing method and apparatus of Patent Document 2 are a hardened and deteriorated layer which ashes a resist mask of a substrate by a plasma processing apparatus having a transparent bell jar which is a transparent dielectric material for UV light. Next, the undegraded layer of the resist mask on the substrate is ashed by irradiating the UV light in an ozone environment.

The method for removing a resist of Patent Document 3 and its apparatus are methods of heating a substrate and causing a blasting phenomenon on the surface of the substrate. Further, after cooling the substrate, the resist is peeled off by an adhesive tape, followed by oxygen plasma, ozone (see Patent Document 4, etc.), or a combination of UV light and ozone. Ashing.

A high dose ion implantation resister forms a hardened layer into a film shape on the surface of the substrate. Since there is a soft resist (unmodified layer) on the substrate of the resist, when the substrate is heated, for example, heated to a temperature higher than 200 ° C, exhaust or thermal expansion by the unaltered layer from the substrate A so-called popping phenomenon in which the surface causes a crack to be scratched. The hardened layer on the surface of the scraped substrate not only contaminates the substrate but also contaminates the chamber in which the substrate is housed.

Therefore, the removal method with heating engineering as exemplified in Patent Document 3 reduces the yield of components obtained from the substrate. It is also necessary to shorten the maintenance cycle of the manufacturing apparatus, which has an influence on the productivity of the substrate.

On the other hand, the processing methods exemplified in Patent Document 1, Patent Document 2, and Patent Document 4 can suppress the blasting phenomenon, but it is necessary to include a plasma generating device. The plasma generating apparatus is expensive, and when the apparatus is provided, the apparatus structure for removing the resist is used to increase the size. This also increases the energy cost when the resist is removed.

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei 8-69896 (paragraphs 0010 to 0016)

Patent Document 2: Japanese Laid-Open Patent Publication No. Hei 8-139004 (paragraphs 0011 to 0023)

Patent Document 3: Japanese Laid-Open Patent Publication No. Hei 9-27473 (paragraphs 0008 to 0011)

Patent Document 4: Japanese Laid-Open Patent Publication No. 2006-294842 (paragraph 0016, 0026)

Therefore, the resist removal method for solving the above-mentioned problems is to supply an ozone gas at a lower pressure than atmospheric pressure, and to supply an unsaturated hydrocarbon gas or a fluorine-substituted gas of an unsaturated hydrocarbon to a reaction system capable of heating the substrate. The resist on the aforementioned substrate is removed.

Further, the resist removing device for solving the above-mentioned problems includes: a chamber for arranging a substrate to be removed as a resist to be heated, and means for supplying ozone gas to the chamber at a lower pressure than atmospheric pressure; A means for supplying an unsaturated hydrocarbon gas or a fluorine-substituted gas of an unsaturated hydrocarbon to the chamber at a lower pressure than atmospheric pressure.

According to the above-described resist removal method and apparatus therefor, the resist removal of the substrate can be performed at 90 ° C or lower. Therefore, even a high-dose ion implantation resist can prevent the occurrence of blasting. Further, since the resist removal of the substrate is performed under a reduced pressure state lower than the atmospheric pressure, safety can be ensured even if a high concentration ozone gas accompanying the explosion is used. Further, damage to the substrate substrate can be reduced. In particular, in the high-dose ion implantation resist, the resist removal can be performed while suppressing the blasting phenomenon. Further, even if there is a substance which is easily oxidized (for example, Cu wiring or the like) in the lower portion of the resist, the oxidation can be suppressed to a minimum.

In the above-mentioned unsaturated hydrocarbon gas, in addition to a hydrocarbon (olefin) having a double bond of carbon exemplified by ethylene, or a hydrocarbon having 3 bonds (alkyne) exemplified by acetylene, Examples are low molecular weight such as butene. The fluorine-substituted gas of the unsaturated hydrocarbon may, for example, be a fluorine-substituted gas of a hydrocarbon exemplified above.

In the above-described method for removing a resist, the ozone gas system is preferably an ultra-high concentration ozone gas obtained by liquefying and separating ozone from a gas containing ozone according to a vapor pressure difference and then gasifying. In the above-described resist removal device, it is preferable that the ozone gas is supplied with an ozone generating device that generates an ultra-high concentration ozone gas by liquefying and separating ozone from a gas containing ozone according to a vapor pressure difference. By using the aforementioned ultra-high concentration ozone gas, the resist can be efficiently oxidized and removed. Further, the aforementioned ozone gas system is not limited to the aforementioned ultra-high concentration ozone gas.

In the resist removal method and the resist removal device, the substrate heating means has a form in which the substrate is supported on a mounting table and the mounting table is heated. For example, a form in which the substrate is heated by irradiating infrared rays onto the mounting table can be mentioned. Further, the heating means of the mounting table is not limited to the light source, and various heating means such as a heater or induction heating may be used, and various heating means such as a heater may be incorporated in the mounting table.

Further, in the resist removal method and the resist removal device, when the substrate is a resist having ion implantation, the ozone gas and the unsaturated hydrocarbon gas or the unsaturated hydrocarbon are washed and washed with ultrapure water. The substrate to be treated with the fluorine replacement gas is preferred. This is because in many cases, ions implanted in a semiconductor manufacturing process form a compound having a low vapor pressure by an oxidation reaction, and even after the resist is completely removed, the compound adheres to the surface of the substrate to form a residue. Since these are formed as water-soluble compounds, they can be easily dissolved in ultrapure water and removed.

Further, in the resist removal method and the resist removal device, when the resist of the substrate is removed, the temperature of the substrate is 90 ° C. When the following method is used to control the internal pressure of the reaction system and the chamber, the phenomenon of blasting can be surely prevented.

According to the above invention, since the resist removal can be performed at a low temperature of 90 ° C or lower, the metal of the substrate base is not oxidized. In particular, it is possible to remove the high-dose ion implantation resist while preventing the occurrence of the blast phenomenon. Further, it is possible to achieve a reduction in energy cost and a simplification of the device structure when the resist is removed.

Fig. 1(a) is a cross-sectional view showing a schematic configuration of a resist removal device 1 according to an embodiment of the invention. Fig. 1(b) is a plan view showing a schematic configuration of the resist removal device 1.

The resist removal device 1 includes a chamber 2, a vacuum pump 3, and a light source 4. The chamber 2 is provided with an ozone gas (O ₃ ) and an unsaturated hydrocarbon gas while accommodating the substrate 16 for removing the resist 17 . The resist 17 may, for example, be a resist for ArF exemplified in Fig. 7; a resist for KrF; a resist for G and I, and the like.

As is clear from the figures 1(a) and 1(b), the chamber 2 is formed in a cylindrical shape. The chamber 2 introduces an unsaturated hydrocarbon gas or a fluorine-substituted gas of an unsaturated hydrocarbon from the side surface portion, and introduces ozone gas from the ceiling portion. The gas system introduced into the chamber 2 is sucked and discharged from the side surface portion opposed to the side surface portion by the vacuum pump 3.

The aforementioned unsaturated hydrocarbon gas system may, for example, be a hydrocarbon having a double bond of carbon (olefin) exemplified as ethylene, or having a triple bond as exemplified by acetylene. Combined hydrocarbon (alkyne). The fluorine-substituted body gas system may, for example, be a fluorine-substituted gas of a hydrocarbon of any of the above. For example, tetrafluoroethylene can be mentioned. The gas supply means of any of the above-mentioned unsaturated hydrocarbon gas or the fluorine-substituted gas system, that is, the gas high-pressure cylinder 6 is introduced through the pipe 5. A fluorine-substituted gas such as a tetrafluoroethylene gas is particularly effective for a hardened ion-implanting resist because it can more effectively remove the effect.

In the case of the aforementioned ozone gas, an ultra-high concentration ozone gas is used. The ozone gas system is introduced from the supply means, that is, the ozone generator 8 via the pipe 7. The pipe 7 is connected to the center of the lid of the sealed chamber 2. The cover seals the chamber 2 via an auxiliary sealing member. As the auxiliary sealing member, an O-ring composed of, for example, an ozone-resistant material such as silicone rubber can be used.

The ultra-high-concentration ozone gas system can be obtained, for example, by liquefying and separating ozone with a gas containing ozone according to a vapor pressure difference. More specifically, for example, ozone gas obtained from an ozone generating apparatus disclosed in JP-A-2001-304756 or JP-A-2003-20209 can be used. The ozone generating device produces ozone gas having an ultrahigh concentration (ozone concentration ≒ 100%) based on a vapor pressure difference between ozone and other gas components (for example, oxygen), and liquefying only ozone. In particular, the ozone supply device of JP-A-2003-20209 includes a plurality of chambers for liquefying and vaporizing only ozone, and the chambers can be continuously supplied with ultra-high concentration ozone gas by controlling the chambers at respective temperatures. Further, a commercially available ozone generator according to the ultrahigh-concentration ozone gas continuous supply method may be, for example, a pure ozone generator (MPOG-HM1A1) manufactured by Tosoh Corporation.

The aforementioned ozone gas system is not limited to the aforementioned ultra-high concentration ozone gas. For example, ozone gas having an ozone concentration of several tens of % or more can be mentioned. Although the ozone gas has high reactivity at atmospheric pressure and is dangerous, in the resist removal device 1, the chamber 2 can be safely treated by the vacuum pump 3 in a reduced pressure state. At atmospheric pressure, the concentration of ozone in the range of 14.3 to 38 vol% is in the field of continuous decomposition, the concentration of ozone in ~44 vol% is in the field of deflagration, and the concentration of ozone in 44 vol% is the field of explosion (Shuguang Handsome, Foundation and Application of Ozone, Guanglin Society, 1996) Year 187).

Fig. 8 shows the case where the Si substrate is ashed only in accordance with various ozone gases (ultra-high concentration ozone gas (ozone concentration ≒ 100%), ozone concentration 8 vol% ozone gas, conventionally-used ozone gas). A characteristic diagram of the relationship between the substrate temperature [°C] and the ashing speed [μm/min]. Fig. 9 shows an Aleni case in the case of ashing a Si substrate based on various ozone gases (ultra-high concentration ozone gas (ozone concentration ≒ 100%), ozone concentration 8 vol% ozone gas, conventional ozone gas) The characteristic diagram of the erg diagram. The ultra-high concentration ozone gas system is produced by an ozone generator (MPOG-HM1A1) manufactured by Mingdian. The conventional system means a case where ashing treatment is performed using an existing ozone-removing agent removing device (Sumke Co., Ltd. UV dry-type photoresist/cleaner UV-300H). This conventional resist removal apparatus irradiates UV light while flowing a low-concentration ozone gas (ozone concentration ≒ 2 vol%) under atmospheric pressure. From this characteristic map, it is clear that the ashing speed (resistance removal efficiency) can be remarkably improved by using an ultra-high concentration ozone gas. In addition, the treatment at 400 ° C using ultra-high concentration ozone gas can remove high dose ion implantation. Resistor (as exemplified in Fig. 4), but it can be confirmed that blasting occurs at a high temperature due to high temperature (as exemplified in Fig. 3), and a small particle is attached to the inside of the chamber. Surface hardened layer.

The vacuum pump 3 sucks the gas in the discharge chamber 2 under a reduced pressure state. The piping 9 connecting the chamber 2 and the vacuum pump 3 includes an exhaust valve 10 and an ozone canceller 11. The exhaust valve 10 can control the opening degree by the control unit 21. The exhaust valve 10 controls the flow rate of the gas in the chamber 2 so that the internal pressure of the chamber 2 becomes a predetermined value. To this end, the chamber 2 is provided with a pressure gauge 19 for detecting the internal pressure. It is preferable to use a dry pump which is resistant to ozone in the vacuum pump 3. This is to avoid a decrease in the life caused by the performance degradation and deterioration due to the possibility of containing ozone in the exhaust gas. The ozone eliminator 11 decomposes ozone contained in the gas sucked from the chamber 2. The ozone eliminator 11 is a known ozone decomposing device used in semiconductor manufacturing technology.

The bottom portion in the chamber 2 is provided with a mounting table 15 via a support member 14 as shown in Fig. 1(a). The substrate 16 for removing the resist 17 is placed on the center of the mounting table 15 as shown in Fig. 1(b). The mounting table 15 is made of SiC and is formed in a substantially disk shape. The mounting table 15 is concentrically arranged with the bottom of the chamber 2. The mounting table 15 is connected to the thermocouple 18. The thermocouple 18 converts the detected thermal energy (temperature) of the mounting table 15 into an electric signal in order to control the temperature of the mounting table 15, and supplies it to the control unit 21. The control unit 21 supplies the light source 4 light intensity control signal based on the electric signal to the light source 4.

The light source 4 heats the substrate 16 by heating the mounting table 15 in the chamber 2. The light source 4 is disposed below the chamber 2. Light source 4 is made of semiconductor The light source for emitting infrared rays used as a heating means in the art can be used. The light source 4 can control the light intensity by the control unit 21. The light source 4 is appropriately provided with a reflection plate 12 for collecting the irradiation light. On the other hand, an opening portion 20 for introducing infrared rays radiated from the light source 4 is provided at the bottom of the chamber 2. Further, the light introduction window 13 is provided to close the opening portion 20. The light introduction window 13 is composed of a material permeable to infrared rays exemplified by artificial quartz.

An operation example of the resist removal device 1 will be described with reference to Figs. 1 and 2 . In a state where the exhaust valve 10 is set to be fully open, the ethylene gas is supplied as an unsaturated hydrocarbon from the gas high-pressure cylinder 6 by the suction force of the vacuum pump 3, and the ultra-high concentration ozone gas (ozone concentration) is taken from the ozone generating device 8. ≒100%) is supplied into the chamber 2. The substrate 16 is held at 80 ° C or lower by the mounting table 15 heated by the light source 4 . Next, the exhaust pump 10 adjusts the opening degree such that the internal pressure of the chamber 2 (the detected value of the pressure gauge 19) is, for example, 400 Pa. In this state, it takes about 5 minutes to process. In the time zone of the treatment, the temperature of the substrate 16 on the mounting table 15 is raised in accordance with self-heating, but is controlled to be 90 ° C or lower. Thereafter, the supply of the ultra-high concentration ozone gas and the ethylene gas is stopped. In the reaction process in the chamber 2, the resist is decomposed by the hydrogen radicals generated by the introduced unsaturated hydrocarbons and ozone, and various other radicals (edited by the Japanese Chemical Society, the quarterly chemical, Chapter 7, Chemistry of Reactive Oxygen, issued on April 20, 1990, pp. 36-37). The composition of the resist 17 composed of hydrocarbons on the substrate 16 is decomposed into carbonic acid gas and water by such a process. Carbonic acid gas and water system become exhaust gases and are interposed The pipe 9 is discharged from the chamber 2.

Fig. 2 is a view showing an example of temporal changes in the stage temperature and the chamber pressure according to the above operation examples. The temperature of the mounting table 15 is stabilized at 80 ° C before the introduction of the ultra-high concentration ozone gas from the ozone generating device 8 (ozone generator MPOG-HM1A1), and the temperature is raised by the reaction heat after the introduction of the ozone gas. It can be confirmed that it ends when it is less than 90 °C.

Fig. 10 is a photograph showing the appearance of the surface of the substrate by the case of the treatment of the embodiment of the resist removal device 1. Specifically, a Si substrate (30 mm × 30 mm) having a resist for KrF in which P (phosphorus) is implanted at 5E15 / cm ² (5 × 10 ¹⁵ /cm ² ) is processed according to the time chart shown in Fig. 2 . Photo of the appearance of the situation. The blasting phenomenon did not occur at the temperature of the mounting table 15 at the maximum temperature of 90 °C. It can be seen that the effect of such a low temperature treatment on the substrate (Si substrate) is very small. Further, as shown in Fig. 11, when the appearance of the copper plate when the copper plate (40 mm × 40 mm) which is very easily oxidized was treated under the same conditions as those of the embodiment of Fig. 10 was observed, no discoloration was observed.

In Fig. 12, the change in the average resist removal rate in the case where the treatment was carried out in the time zone of 2 minutes to 5 minutes under the same processing conditions as above was shown. The sample was prepared by ion implantation in a g-line resist containing a phenol resin as a main component, and in the case of ion-injecting a KrF resist (the ion implantation system is the same as the embodiment of the 11th embodiment). ). There was not much difference in the processing time of 2 to 4 minutes, but the processing in 5 minutes became very rapid. This system is considered to be 2~4 minutes to remove the surface The hardened layer is 4 to 5 minutes to remove the unhardened, unaltered layer of the substrate. No matter what kind of sample was completely removed at 5 minutes. The difference in the removal speed at this time is based on the difference in the original thickness. Further, when the surface after each time treatment was observed, it was confirmed that the surface was discolored with time (after 2 minutes, after 3 minutes, after 4 minutes, and after 5 minutes), and the thickness of the resist film was changed.

On the other hand, Fig. 4 is a photograph showing the appearance of the surface of the substrate treated by the resist removal method of the comparative example. Specifically, for a Si substrate having a resist for KrF in which P (phosphorus) is implanted at 5E15/cm ² (5 × 10 ¹⁵ /cm ² ), the temperature of the mounting table 15 is only 400 ° C. Photograph of the appearance in the case where the concentration of ozone gas is treated. Although the resist can be removed by this method, it is confirmed that the blasting occurs due to the high temperature, and a resist hardening layer which becomes a fine film-like particle is attached to the inside of the chamber. Further, it was confirmed that a blasting phenomenon occurred in the ozone gas alone treatment system in which the ozone concentration of 8 vol% of the ozone at the temperature of the mounting table 15 was 400 ° C (Fig. 3).

Fig. 5 is an enlarged photograph (magnification: 400 times) of the surface of the resist boundary portion of the substrate treated by the resist removal method of the example. It was found that there was no film-like peeling material, and no blasting of the generated particles occurred.

Fig. 6 is an enlarged photograph (magnification: 400 times) of the surface near the center portion of the substrate treated by the resist removal method of the example. Although it is considered that there is residue on the surface near the center portion, it can be confirmed that the surface of the resist boundary portion is significantly smaller than that of Fig. 5. The residue tends to increase as the elapsed time elapses from the chamber, and can be removed by washing with ultrapure water. Therefore, this is not a resist residue, but is considered to be an oxidized ion (here, P ₂ O ₅ or P ₂ O ₃ ) in the implanted resist. This is considered to be an implanted ion used in semiconductor manufacturing engineering. In many cases, a water-soluble compound having a low vapor pressure is formed by oxidation, and remains on the substrate after being processed. After being taken out from the chamber, it is adsorbed in the atmosphere. The moisture is observed as a surface residue.

1‧‧‧Rejection removal device

2‧‧‧ chamber

3‧‧‧vacuum pump

4‧‧‧Light source

5‧‧‧Pipe

6‧‧‧ gas high pressure cylinder

7‧‧‧Pipe

8‧‧‧Ozone generating device

9‧‧‧Pipe

10‧‧‧Exhaust valve

11‧‧‧Ozone eliminator

12‧‧‧reflector

13‧‧‧Light introduction window

14‧‧‧Support members

15‧‧‧mounting table

16‧‧‧Substrate

17‧‧‧Resist

18‧‧‧ Thermoelectric

19‧‧‧ pressure gauge

20‧‧‧ openings

21‧‧‧Control Department

Fig. 1(a) is a cross-sectional view showing a schematic configuration of a resist removal device according to an embodiment of the invention, and Fig. 1(b) is a front view showing a schematic configuration of a resist removal device.

Fig. 2 is a graph showing changes with time in the stage temperature and the chamber pressure of the resist removal device according to the embodiment of the invention.

Fig. 3 is a photograph showing the appearance of the surface of the Si substrate treated by the resist removal method of the comparative example (only 8% ozone gas).

Fig. 4 is a photograph showing the appearance of the surface of the Si substrate treated by the resist removal method of the comparative example (only 100% ozone gas).

Fig. 5 is a magnified surface (magnification: 400 times) of the resist boundary portion of the substrate treated by the resist removal method of the inventive example.

Fig. 6 is an enlarged photograph (magnification: 400 times) of the surface near the center portion of the substrate treated by the resist removal method of the inventive example.

Figure 7 is the molecular structure of various resists.

Fig. 8 is an ozone gas using only various ozone gases (ultra-high concentration ozone gas (ozone concentration ≒ 100 vol%)), ozone concentration 8 vol%, A characteristic diagram of the relationship between the substrate temperature [° C.] and the ashing rate [μm/min] in the case of ashing the Si substrate with respect to the conventional ozone gas.

Fig. 9 is a view showing a case where only a variety of ozone gases (ultra-high concentration ozone gas (ozone concentration ≒ 100 vol%)), ozone concentration 8 vol% ozone gas, and conventional ozone gas) are used to ash a Si substrate. The characteristic diagram of the Leonier chart.

Figure 10 is a photograph of the appearance of the surface of the substrate treated with respect to the examples.

Fig. 11 is a photograph showing the appearance of the surface of the copper plate treated with respect to the examples.

Fig. 12 is a graph showing changes in the average resist removal speed in the case of treatment in a belt having a treatment time of 2 minutes to 5 minutes.

1‧‧‧Rejection removal device

2‧‧‧ chamber

3‧‧‧vacuum pump

4‧‧‧Light source

5‧‧‧Pipe

6‧‧‧ gas high pressure cylinder

7‧‧‧Pipe

8‧‧‧Ozone generating device

9‧‧‧Pipe

10‧‧‧Exhaust valve

11‧‧‧Ozone eliminator

12‧‧‧reflector

13‧‧‧Light introduction window

14‧‧‧Support members

15‧‧‧mounting table

16‧‧‧Substrate

17‧‧‧Resist

18‧‧‧ Thermoelectric

19‧‧‧ pressure gauge

20‧‧‧ openings

21‧‧‧Control Department

Claims (9)

A method for removing a resist, characterized in that an ozone gas is supplied at a lower pressure than atmospheric pressure, and a fluorine-substituted gas of an unsaturated hydrocarbon gas or an unsaturated hydrocarbon is supplied to a reaction system capable of heating the substrate, and the substrate is removed. Resistor. The method for removing a resist according to the first aspect of the invention, wherein the ozone gas system is an ultra-high concentration ozone gas obtained by liquefying and separating ozone from a gas containing ozone according to a vapor pressure difference and then gasifying. The method of removing a resist according to claim 1 or 2, wherein the substrate is supported on a mounting table, and the substrate can be heated by irradiating the mounting table with infrared rays. The method of removing a resist according to the first aspect of the invention, wherein, in the case where the substrate is an ion implantation resist, the ozone gas and the unsaturated hydrocarbon gas are supplied at a lower pressure than atmospheric pressure, and then washed with ultrapure water. Clean the aforementioned substrate. The method of removing a resist according to the first aspect of the invention, wherein the internal pressure of the reaction system is controlled such that the temperature of the substrate reaches 90° C. or less when the resist on the substrate is removed. A resist removal device characterized by comprising: a chamber capable of accommodating a substrate for resist removal; a means for supplying ozone gas to the chamber at a lower pressure than atmospheric pressure; and a lower pressure than atmospheric pressure Supply of unsaturated hydrocarbon gas or unsaturated hydrocarbon A means by which a fluorine replaces a gas to the chamber. The apparatus for removing a ozone gas according to the sixth aspect of the invention, wherein the ozone gas is supplied by using an ultra-high concentration ozone gas generated by liquefying and separating ozone from a gas containing ozone according to a vapor pressure difference. An ozone generating device is carried out. The apparatus for removing a resist according to claim 6 or 7, wherein the chamber includes: a mounting table that supports the substrate; and a light source that irradiates the mounting table with infrared rays to heat the substrate. The apparatus for removing a resist according to claim 6, wherein the chamber controls the internal pressure such that the temperature of the substrate reaches 90 ° C or lower.