JPH1055992A - Cleaning method and semiconductor manufacturing method - Google Patents

Abstract

(57) Abstract: Provided is a cleaning method capable of efficiently removing deposits in a semiconductor manufacturing apparatus and contamination on the surface of a semiconductor substrate. A method for manufacturing a semiconductor device that removes contamination on a substrate surface by using the present method, and a method for manufacturing a semiconductor device using a manufacturing device after removing deposits in the device are provided. A cleaning gas 2d in a cylinder 1d is made of a gas containing at least one of BrF ₃ and BrF ₅ and BrF ₇ , and is introduced into a semiconductor manufacturing apparatus 6 from an inlet 5. The cleaning gas 2d is decomposed into halogen radicals by the heat given by the external heater 9. At this time, the contaminants on the inner wall 8 or the semiconductor substrate 12 of the semiconductor manufacturing apparatus react with these radicals, evaporate, and are removed from the exhaust port 13, so that these attached substances or contaminants can be efficiently cleaned.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cleaning method and a method for manufacturing a semiconductor device.

[0002]

2. Description of the Related Art In recent semiconductor manufacturing, thermal CVD, plasma CVD, and dry etching processes have become increasingly important. In these processes, various gases are introduced into a manufacturing apparatus, and film formation and etching are performed using a gas phase reaction and a surface reaction of the gas. For example, plasma C
In the film formation by VD, gas molecules are dissociated into radicals having high reactivity for the purpose of film formation at a higher speed with the aim of improving semiconductor production per unit time: throughput. In dry etching for forming a contact hole, an etching process with high selectivity has been developed with the aim of generating a groove having a high aspect ratio. Also in this process, gas molecules are decomposed into radicals having high deposition performance in order to protect portions other than the material to be etched. Therefore, even when the film is formed and etched only on the wafer, radicals with high adhesion are deposited on the inner wall of the container. When such a deposited film adheres to the inner wall of the manufacturing apparatus, particles are generated inside the apparatus, the adhered substance is peeled off, and the film forming and etching performance deteriorates with time. Kimono needs to be removed.

[0003] Methods for removing these deposits include (1) mechanical polishing, (2) wet cleaning using an acid or alkali aqueous solution, and (3) plasma such as NF ₃ , CF ₄ , SF ₆ , O _2, etc. (4) A thermal cleaning method using ClF ₃ is generally used. Here, (1) and (2) require that the apparatus be disassembled for each cleaning, which reduces the semiconductor production yield: throughput. On the other hand, in (3), plasma is generated, and adhesion in the manufacturing apparatus is removed by radicals generated by dissociation of gas. In the cleaning method using the plasma, the removal rate is low except for the region where the plasma is generated, so that the plasma must be generated for a long time. Therefore, this method also reduces the throughput of the semiconductor. Also,
Prolonged plasma irradiation causes deterioration of the manufacturing apparatus. Poly-S inside the container only by heating without using plasma
As a method for removing deposits containing i, metal and SiO ₂ , a cleaning method (4) using ClF ₃ has been proposed as disclosed in Japanese Patent Application Nos. 17857/64 and 146681/1991. ing. Here, ClF ₃ is decomposed into ClF and F ₂ by the reaction with F ₂ at 220 ° C. or higher, and the F radical generated by further heating has an excellent adhering matter removing performance. Since this method can clean the inside of the apparatus in a short time without damaging the inside of the apparatus without generating plasma, it is currently being vigorously applied as a cleaning method in a semiconductor manufacturing apparatus.

On the other hand, a gas composed of molecules composed of Br and F is used for a selective etching of a substrate (Japanese Patent Application No. 60-53027) and a cleaning gas mixed with NF ₃ (Japanese Patent Application No. 3-146681). The present invention is used for etching a SiN film (Japanese Patent Application No. 4-10621) and for etching before and after formation of a conductor film (Japanese Patent Application No. 5-146681). However, there is no known example of a method for cleaning a deposit or an adhering matter in which many substances are intricately combined in a semiconductor device and on a surface of a semiconductor wafer with a gas composed of molecules composed of Br and F alone.

[0005] In recent years, the degree of integration of integrated circuits formed on the surface of a substrate such as a semiconductor wafer has been increasing more and more, and the line width of the pattern has been reduced. The minimum processing dimension is
It is 0.3 μm for 64 Mbit DRAM and 0.2 μm for 256 Mbit DRAM, and a very small amount of contamination in the manufacturing process significantly lowers product quality and yield. Of particular concern as trace contamination are metal contamination, organic contamination and natural oxide films.

As a means for cleaning the substrate surface against the above contamination, RCCA Review 31 (1970) No. 18
From page 7 to page 207 [RCA Review, 31 (1970) P.1
87-206], a method of heating a mixture of aqueous ammonia and aqueous hydrogen peroxide to about 80 ° C. and dipping the wafer into the mixture (RCA cleaning) is generally performed.
Since these wet cleaning methods are processed in a liquid, it is expected that the limit will be imposed sooner or later due to the fact that re-adhesion of contamination is inevitable and the liquid does not sufficiently penetrate into high steps or complicated element structures. Have been. Accordingly, a cleaning method utilizing a gas phase reaction and a surface reaction of a gas, in which reattachment of contamination cannot occur in principle and which can easily clean a high step portion, has been proposed. This is called dry cleaning, and as described in JP-A-64-9621, a method of removing metal contamination on a Si wafer by irradiating ultraviolet light to chlorine gas. As described in the official gazette, plasma is applied to oxygen gas to
There are known a method of removing organic substances on an i-wafer and a method of removing a natural oxide film on a wafer by applying plasma to a fluorine-based gas as described in JP-A-1-77120.

[0007]

However, the above-mentioned known technique has the following problems.

[0008] In the method of introducing plasma-free ClF ₃ into a vessel and heating, the cleaning speed greatly differs depending on the type of film. For this reason, ClF ₃ does not yet have sufficient removal performance for deposits in an apparatus in which many substances are complexly combined, and a gas having a higher removal performance may be required.

The cleaning gas obtained by mixing NF ₃ and BrF-based gas is effective only when it is treated in plasma. However, as described above, cleaning using plasma requires a long time, so that the throughput of semiconductor device production is low. There was a problem of lowering. On the other hand, in the case of wafer cleaning, processing technology such as dry etching technology has advanced with the miniaturization of semiconductor elements, and contamination having an unprecedented complex composition has been generated through complicated reactions in plasma. It is expected that the dry cleaning method will not be able to remove at all.
Therefore, in order to manufacture a semiconductor device such as a semiconductor integrated circuit at a high yield, a method of removing contamination on a substrate having a complicated composition is indispensable.

An object of the present invention is to provide a cleaning method for removing adhering matter in a semiconductor device, which has a removal capability equal to or higher than that of a ClF ₃ thermal cleaning method, and a cleaning method capable of removing contamination of a semiconductor substrate. Is to provide.

[0011]

According to the present invention, a gas containing at least one of BrF ₃ , BrF ₅ and BrF ₇ (hereinafter referred to as a cleaning gas) is provided in a semiconductor manufacturing apparatus. A cleaning method is provided which removes deposits in the semiconductor manufacturing apparatus or contamination on the semiconductor surface by heating while supplying the semiconductor manufacturing apparatus to a temperature range of 650 ° C. or lower.

[0012] Preferably, in the above-mentioned cleaning method, a cleaning method is provided in which a region for heating the semiconductor manufacturing apparatus is limited to a region where a deposit exists.

Preferably, in the cleaning method, a cleaning method is provided in which a rare gas is added in addition to the cleaning gas.

Preferably, in the above-mentioned cleaning method, there is provided a cleaning method for removing contamination on a semiconductor substrate or a semiconductor back surface.

Preferably, in the above-mentioned cleaning method, there is provided a cleaning method for removing a residue on the semiconductor wafer surface after the etching treatment of the semiconductor wafer surface.

Preferably, in the cleaning method, Si
The present invention provides a cleaning method for removing contamination on a semiconductor surface or a contamination on a semiconductor wafer adhered to an insulator, an organic substance, or a metal.

Preferably, in the cleaning method, there is provided a cleaning method for removing contamination on the semiconductor surface by irradiating an ultraviolet ray, a laser beam, or a radiation beam into the manufacturing apparatus together with the introduction of the cleaning gas.

Preferably, in the above-mentioned cleaning method, there is provided a cleaning method in which the cleaning gas is stored at a low temperature before use and is heated only when used.

Preferably, there is provided a cleaning method in which the cleaning gas is stored in a liquid state, and is heated and vaporized only at the time of use.

Further, in order to achieve the second object, the present invention provides a semiconductor device for processing a semiconductor substrate surface by supplying the cleaning gas into a semiconductor manufacturing apparatus and heating the semiconductor manufacturing apparatus. A manufacturing method is provided.

According to the present invention, in order to achieve a third object, the cleaning gas is supplied into a semiconductor manufacturing apparatus, and the inside of the apparatus is cleaned by heating the semiconductor manufacturing apparatus. A method for manufacturing a semiconductor device for processing a semiconductor substrate using the device is provided.

In the present invention configured as described above, BrF
₃ and a gas containing at least one of BrF ₅ and BrF ₇ (hereinafter referred to as a cleaning gas) is supplied into the semiconductor manufacturing apparatus, and when the semiconductor manufacturing apparatus is heated, BrF _n → BrF _n−2 + F _2. , BrF _n → BrF _n-1 +
Decomposes like F. The rate of the decomposition reaction increases as the temperature T during heating increases. Here, the rate of the decomposition reaction activation energy of E _A, and the Boltzmann constant k _B ex
proportional to _{p (-E A / k B T} ).

FIG. 1 shows the electron affinities and excitation energies of various gases and radicals based on molecular orbital calculations. Here, the electron affinity is a measure of the ease of electron absorption, and the excitation energy is a measure of the energy required for decomposition. Therefore, the higher the reactivity of the molecule and radical goes to the upper left in this figure, which is consistent with the tendency of the existing experiment. on the other hand,
In the figure, the lower the right, the more stable and easy to handle, so these are candidates for the cleaning gas. The order of ease of handling is as follows. BrF ₃ >ClF> BrF ₅ >
ClF ₃ > BrF ₇ , where electron affinity is higher than ClF and ClF ₂ generated by decomposition of ClF ₃ (1) BrF and BrF ₂ generated by decomposition of BrF ₃ are Br
F <ClF, BrF ₂ <ClF ₂ (2) BrF ₄ and BrF ₃ generated by decomposition of BrF ₅ are BrF ₃ <ClF, BrF ₄ > ClF ₂ (3) BrF ₅ and BrF ₆ generated by decomposition of BrF ₇ Are BrF ₅ > ClF and BrF ₆ > ClF ₂ . The larger the electron affinity of the radical generated by the decomposition, the easier it is to absorb electrons from the bond orbital of the attached matter, so that the attached matter is easily decomposed. Most of the decomposed deposits are removed as halides. Accordingly, the ability to remove the deposits from (1) to (3) is as follows.

BrF ₇ > ClF _{3 to} BrF ₅ > BrF
₃ Therefore, a gas having an adhering substance removing ability equal to or higher than that of ClF ₃ heat cleaning is BrF ₇ and BrF ₅ , and a gas having an adhering substance removing ability equal to or less than ClF ₃ heat cleaning is B
rF ₃ and BrF ₅ can be used.

These Br-based gases (BrF ₃ , BrF ₅ ,
As a feature of the (BrF ₇ gas), the cleaning performance increases as the temperature rises (described above). However, at a high temperature, the dissociation of these gases proceeds, and the BrF radical having low reactivity (FIG. 2)
And the cleaning performance deteriorates. Also,
Furthermore, when the temperature of the apparatus is increased, Br radicals are generated, so that a Br compound having low sublimability is deposited on the surface of the wafer, which may lower the cleaning performance. Also,
From the viewpoint of the cost of the apparatus itself and the running cost, the apparatus temperature is preferably as close to room temperature as possible. From the above, it is appropriate that the reaction temperature be equal to or lower than the temperature (T) at which the ratio of BrF and Br radicals increases. According to calculations, T
Was found to be approximately 650 ° C.

On the other hand, any gas other than the gas in the cleaning gas region shown in FIG. 1 (a region classified as a gas having an electron affinity and an excitation energy suitable for cleaning according to the concept of the present invention) is used in the present invention. Clearly included.

As described above, when the apparatus is heated, a heating apparatus and electric power for heating are required. At this time, if only the area where the deposits are present is heated without heating the entire apparatus, the cost of the apparatus itself and the running cost can be reduced.

Further, by adding a rare gas to the cleaning gas, the reactivity per unit volume is reduced and handling becomes easy.

Further, radicals decomposed by the cleaning substance deprive electrons of bonding of contaminated portions on the semiconductor substrate, decompose attached substances, and mostly sublimate as halides. Thereby, the deposits on the semiconductor substrate or on the back surface can be removed.

As described above, the residue on the surface of the semiconductor wafer after the etching of the surface of the semiconductor wafer can be removed.

Further, as described above, contamination on the surface of a semiconductor made of Si or contamination on a semiconductor wafer covered with an insulator, an organic substance, or a metal can be removed.

By irradiating ultraviolet light, laser light, or radiation light on the semiconductor substrate or the back surface together with the introduction of the cleaning substance, the decomposition of the gas cleaning substance is promoted, and the decomposed radicals are excited. And the performance of removing adhering substances on the semiconductor substrate or on the back surface can be improved.

Further, the cleaning substance is stored at a low temperature before use, and is used only at the time of use, and the reactivity is suppressed until immediately before use. And the use at a high temperature improves the performance of removing adhering substances.

Further, the cleaning substance is stored in a liquid state, and is heated and vaporized only at the time of use, thereby facilitating handling before use.

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION

(Embodiment 1) A first embodiment of the present invention will be described with reference to FIGS. The apparatus of the present embodiment shown in FIG. 2 is a thin film manufacturing apparatus that causes a gas phase chemical reaction by heating to form a thin film on a semiconductor substrate. When forming a film, the gas 2a for film formation of the cylinder 1a is controlled by the valve 3a and the mass flow controller 4a, and is introduced into the thin film production container 6 through the gas inlet 5. At this time, the gas 2a for film formation is decomposed and reacted by the heat applied from the outside of the thin film production container 6, and a thin film is formed on the semiconductor substrate 12 of the holder 7.

At this time, the same thin film as on the semiconductor substrate adheres to the inner wall 8 of the container. The deposits need to be removed because they hinder film formation on the semiconductor substrate due to peeling or the like.

For this purpose, the cleaning BrF ₇ gas 2d in the cylinder 1d is controlled by the valve 3d and the mass flow controller 4d, and is introduced into the thin film production container 6 through the gas inlet port 5. At this time, the BrF ₇ gas In order to dilute 2d, the He gas 2e in the cylinder 1e is also controlled by the valve 3e and the mass flow controller 4e.
The gas is introduced into the thin film production container 6 through the gas inlet 5. Then, the BrF ₇ gas 201 for cleaning is decomposed by the heat applied from the heater 9 outside the thin film manufacturing container 6. The molar ratio of BrF ₇ gas to He gas is 1: 1. The radicals generated by the decomposition react with the deposits on the wall,
The compound becomes a highly volatile compound, is sucked by the exhaust pump 10 and is exhausted to the outside of the thin film production container 6, and is eliminated by the elimination device 11. Then, the supply, the exhaust, and the heating of the BrF ₇ gas and the He gas are continued until the deposit on the inner wall 8 of the container is removed.

In order to estimate the effect of this embodiment, (1)
Poly-Si film on the inner wall of the vessel, Si-N film, SiO ₂ film, WS
An i film and a W film were formed, and (2) a BrF ₇ gas and a He gas were supplied and heated, and the removal rates (etching rates) of the various thin films were examined. FIG. 3 shows the etching rates of various films by BrF and ClF ₃ when the temperature was changed.

FIG. 3 shows that BrF ₇
It can be seen that the etching rate of the Poly-Si film, the Si-N film, and the SiO ₂ film by the gas is higher than the etching rate by the ClF ₃ gas. This is because the electron affinity of BrF ₆ and BrF ₅ generated by the decomposition of BrF ₇ (the ability to absorb electrons relating to the binding of the attached matter) is greater than the electron affinity of ClF ₂ and ClF generated by the decomposition of ClF ₃ , respectively. This can be explained. At 650 ° C. or lower, the cleaning performance increases as the temperature increases, but at 650 ° C. or higher, the cleaning performance does not change or decreases even when the temperature increases. This can be explained by the fact that the ratio of BrF radical having low cleaning performance increases at 650 ° C. or higher. In addition, it is considered that Br radicals are generated, and Br compounds having low sublimability are deposited on the surface of the wafer, and cleaning performance is deteriorated.

(Embodiment 2) FIG. 4 shows a second embodiment of the present invention.
This will be described with reference to FIG. When the cleaning gas BrF ₇ used in the first embodiment is changed to BrF ₃ and BrF ₅ ,
FIG. 4 shows the result of study on the etching rate of the Poly-Si film. The experimental apparatus and conditions are the same as in Example 1 except for the cleaning gas. FIG. 4 shows that the etching rates of the various gases are in the order of BrF ₇ > ClF _{3 to} BrF ₅ > BrF ₃ . Also, a Si—N film, a SiO ₂ film, a WSi
The etching rate of BrF ₃ , BrF ₅ , and Br ₇ is the same for the film and the W film as described above, and the most suitable gas type can be selected for the application destination.

(Embodiment 3) A third embodiment of the present invention will be described below. TiW-Al-T using Cl ₂ and SF ₆ gas
According to EPMA analysis (analysis of contained elements from characteristic X-rays generated at the time of electron beam irradiation) and SEM observation, the semiconductor wafer surface after the dry etching by the microwave of iW was A
A residue (etching residue) composed of 1, Ti, W, O, and Si was deposited to a thickness of about 0.1 μm. Therefore, the present wafer is placed on the holder 7 and the flow rate ratio is 1:
The first BrF ₅ and He gas were introduced into the apparatus from the outside, and heated by the external heater 9. After the main cleaning process, when the surface of the main wafer is examined again by SEM,
Most of the etching residue has disappeared. At this time, in order to suppress damage to the substrate due to the temperature rise, the temperature in the container is set to be about 100 degrees lower than the cleaning temperature in the apparatus of the fourth embodiment. When ClF ₃ was used as the cleaning gas instead of BrF _{3 and} the other conditions were the same, the Si substrate of the present wafer was damaged.

(Embodiment 4) In a semiconductor manufacturing line, contamination accumulates when the back surface comes into contact with a transport system or a tool, and the contamination is transferred to a wafer or heated in a subsequent wet cleaning step or the like. In many cases, the device characteristics are remarkably deteriorated by being diffused to the surface of the wafer. When the contamination on the back surface of the wafer in the actual production line was measured by EPMA, each element of Al, O, Ti, W, Fe, and Ni was observed. BrF ₅ and He with a flow ratio of 1: 1 were introduced into the apparatus shown in FIG. Again, the back of the wafer is EP
When measured by MA, almost no element was observed before the treatment, and it was found that the present invention was also effective for cleaning the back surface of the wafer.

(Embodiment 5) A fifth embodiment of the present invention is shown in FIG.
It will be described according to. The apparatus of the present embodiment shown in FIG. 5 is the same as the apparatus of FIG. 1 in the first embodiment, except that a part of the upper surface in the container 6 is provided above the quartz plate 14 with the ultraviolet irradiation device 20.
Further, the ClF ₃ gas 2f in the cylinder 1f is
f, 3h and the mass flow controller 4f, and can be introduced into the container 6 through the gas introduction port 5.

In order to estimate the effect of ultraviolet irradiation, a poly-Si film is placed on the holder 7 and the flow ratio of BrF ₅ is 1: 1.
And He were introduced into the apparatus and heated by the heater 9.
At this time, when the ultraviolet light of 200 nm was irradiated from above at 1 kw, the etching rate of the poly-Si film was increased about 1.3 times as compared with the case without irradiation. This is due to the irradiation
With decomposition promotes the BrF _5, because the decomposition and removal of the poly-Si film by radicals generated by the decomposition of BrF ₅ is promoted.

(Embodiment 6) FIG. 6 shows a sixth embodiment of the present invention.
It will be described according to. BrF ₅ and BrF ₇ are highly reactive and react at room temperature with the introduction device before being introduced into the container,
The introduction device may be corroded and the reactivity of these gases may be degraded. For this reason, in FIG. 7, the cleaning gas introduction system is surrounded by a heat insulating material 18, and is kept at a low temperature by the cooling device 17 so as not to react with the introduction device. In the case where the cleaning material is liquid at room temperature, the cleaning material is heated to a temperature equal to or higher than the vaporization temperature by the heating device 19 immediately before the introduction port to be vaporized.

[0046]

According to the present invention, BrF ₃ and BrF ₅
Cleaning gas composed of gas molecules containing at least one of BrF ₇ and BrF ₇ is decomposed by heating into radicals that easily absorb electrons involved in bonding of attached matter. Decomposes and decomposes attached substances and contaminants, and removes them from the manufacturing equipment. The ability to remove deposits is BrF ₇
> ClF _{3 to} BrF ₅ > BrF ₃ , and optimal cleaning can be performed by selecting a type according to the application destination.

Therefore, for example, the deposits in the manufacturing apparatus generated in various film forming processes are removed by BrF which is a cleaning gas.
By introducing and heating ₇ , it can be removed at a higher speed than the ClF ₃ thermal cleaning. This does not use plasma,
Damage due to plasma irradiation of the manufacturing apparatus can be reduced, and the cleaning process time can be shortened compared to ClF ₃ thermal cleaning.

In the dry etching in the semiconductor device manufacturing process, an etching residue is left on the substrate surface. This residue can be removed by introducing and heating BrF ₅ or BrF ₃ as a cleaning substance. This makes it possible to remove resist residues that are difficult to remove by wet cleaning.

As described above, according to the present invention, the manufacturing cost of a semiconductor device can be reduced and the throughput in manufacturing a semiconductor device can be improved.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of electron affinities and excitation energies of various gases and radicals by molecular orbital calculation.

FIG. 2 is a system diagram of a thin film manufacturing apparatus for generating a thin film on a semiconductor substrate by causing a gas phase chemical reaction by heating, and an apparatus for cleaning adhered substances in the apparatus using BrF ₇ and He.

FIG. 3 is a characteristic diagram showing the etching rates of various films by BrF ₇ and ClF ₃ when the temperature is changed.

FIG. 4 shows BrF ₃ , BrF ₅ , and B when the temperature is changed.
FIG. 4 is a characteristic diagram showing an etching rate of a Si film by rF ₇ .

FIG. 5 is a system diagram showing a thin film manufacturing apparatus for forming a thin film on a semiconductor substrate by causing a gas phase chemical reaction by heating and an apparatus for cleaning a contaminated portion on a semiconductor substrate using BrF ₅ and He.

FIG. 6 shows a thin film manufacturing apparatus for forming a thin film on a semiconductor substrate by causing a gas phase chemical reaction by heating, and cleaning of deposits in the apparatus using BrF ₇ which is cooled during storage and gasified only during use. FIG.

[Explanation of symbols]

1a to 1f: cylinder, 2a, 2b: gas for film formation, 2c
_{... ClF 3, 2d ... BrF 7} , 2e ... He, 2f ... Br
F ₃ , 3a to 3h valves, 4a to 4f mass flow controllers, 5a to 5c gas inlets, 6 vessels, 7 ...
Holder, 8: Container inner wall, 9: Heater for heating, 10: Exhaust pump, 11: Excluding device, 12: Semiconductor substrate, 13: Gas exhaust port.

Claims (11)

[Claims] 1. A gas containing at least one of BrF ₃ , BrF ₅ , and BrF ₇ is supplied into a semiconductor manufacturing apparatus, and the semiconductor manufacturing apparatus is heated to a temperature range of 650 ° C. or less. A cleaning method characterized by removing deposits in a semiconductor manufacturing apparatus or contamination on a semiconductor surface. 2. The cleaning method according to claim 1, wherein an area where the semiconductor manufacturing apparatus is heated is limited to an area where a deposit exists. 3. The cleaning method according to claim 1, wherein a rare gas is added in addition to the cleaning gas. 4. The cleaning method according to claim 1, wherein contamination on the semiconductor substrate or the back surface of the semiconductor is removed. 5. The cleaning method according to claim 1, wherein a residue on the surface of the semiconductor wafer after the etching of the surface of the semiconductor wafer is removed. 6. The cleaning method according to claim 1, wherein the manufacturing apparatus is irradiated with ultraviolet light, laser light, or radiation light together with the introduction of the cleaning gas. 7. The cleaning method according to claim 1, wherein the cleaning gas is stored at a low temperature before use and is heated only when used. 8. The cleaning method according to claim 1, wherein the cleaning gas is stored in a liquid state, and is heated and vaporized only when used. 9. The cleaning method according to claim 1, wherein contamination on a semiconductor surface composed of Si or contamination on a semiconductor wafer applied to an insulator, an organic substance, or a metal is removed. 10. The method of manufacturing a semiconductor device according to claim 1, wherein the cleaning gas is supplied into the semiconductor manufacturing apparatus, and the surface of the semiconductor substrate is processed by heating the semiconductor manufacturing apparatus. 11. The semiconductor according to claim 1, wherein the cleaning gas is supplied into the semiconductor manufacturing apparatus, and the inside of the apparatus is cleaned by heating the semiconductor manufacturing apparatus, and then the semiconductor substrate is processed using the apparatus. Device manufacturing method.