JP6568457B2 - Plasma processing method - Google Patents

Description

  The present invention relates to a plasma processing method.

  With the recent high integration and high speed of semiconductor integrated circuits, the gate size of high speed logic devices will reach the 10 nm level in the next few years, and the processing dimensional accuracy of Å level (3σ = 1 nm or less) is required. . Slight variations in gate electrode dimensions cause large fluctuations in source / drain current and standby leakage current values, so stabilization of the processing shape such as gate electrode dimension (CD: Critical Dimension) accuracy is important for improving yield. It is a necessary requirement.

One factor that affects the processing shape (CD accuracy, shape anisotropy, material selection ratio, etc.) is the deposition of etching reaction products on the surface of the processing chamber. It has been elucidated by gas phase measurement in plasma that even if plasma is generated under the same conditions depending on the presence or absence of deposits, radical consumption and radical recombination probability on the surface of the processing chamber change significantly. For example, Non-Patent Document 1 discloses that the amount of Cl radicals in the Cl ₂ plasma varies several times depending on the presence or absence of SiCl _x deposits on the surface of the processing chamber. If the radical density in the plasma changes, the machining shape also changes. Further, there are various kinds of reaction products at the time of processing depending on materials and gas types used for transistors. In recent years, in order to improve transistor characteristics, a transition from a conventional Poly-Si / SiO ₂ structure to a High-K / MetalGate structure and a transition from a planar transistor to a three-dimensional transistor structure are progressing. For this reason, the types of materials used for transistors (for example, metallization of gates, use of high-K gate insulating film materials, III-V channel, etc.) are diversified, and hardly volatilize deposited on the processing chamber surface. The types of functional materials and their cleaning methods are also diversifying. Non-Patent Document 2 discloses a relation between Ti deposits on the surface of the processing chamber and process variations, a Ti cleaning method that causes process variations, and the like. If metal cleaning is performed appropriately, process fluctuations can be suppressed.

  Another important factor for improving the yield is suppression of pattern defects. Causes of pattern defects in the etching processing apparatus are caused by reaction products including a part of the wafer and gas on the surface of the processing chamber, processing chamber surface members caused by scraping and corrosion of the processing surface members, and composites thereof. is there. Due to the processing chamber surface member, it becomes a problem particularly when the member contains a non-volatile substance containing a metal or a lanthanoid compound. Once the non-volatile material is shaved, it may fall directly onto the wafer, or once attached to the surface of the processing chamber that is different from the shaved place or member, it grows with the progress of mass production processing and peels off at some point on the wafer. It is because it falls to. Since the fallen object acts as a mask that hinders etching of the lower layer of the wafer, a pattern defect is generated and the yield of the product is reduced. Such a substance that inhibits etching is called foreign matter. As the gate dimension is reduced, the allowable particle size and the number of foreign particles are decreasing year by year, and the mass production process is becoming more severe.

  In summary, in order to improve the yield of mass production, an etching technique that achieves both stabilization of the processing shape and reduction of foreign matters is required. The stabilization of the processing shape has a close relationship with deposits on the surface of the processing chamber, and the reduction of foreign matter has a close relationship with scraping and corrosion of the processing chamber surface members in addition to the deposits on the processing chamber surface.

  Conventionally, a technique for keeping the surface state of a processing chamber constant by using a plasma cleaning process or a seasoning process for each wafer process or lot has been studied. Further, Patent Document 1 discloses a technique for reducing the influence on process variation caused by a change in the processing chamber surface state by performing a coating for depositing a film containing CF or Si on the processing chamber surface. Further, Patent Document 2 uses an after-treatment method that can reduce foreign matters caused by a coating film containing Si and a metal-compatible cleaning that can reduce process variations caused by metal reaction products deposited on the surface of the processing chamber. Technology is disclosed.

US Patent 7,204,913 JP 2014-53644 A

S. J. Ullal, T. W. Kim, V. Vahedi, and E. S. Aydil, J. Vac. Sci. Technol., A 21, 589 (2003). Kosa Hirota, Naoshi Itabashi and Junichi Tanaka, J. Vac. Sci. Technol., A 32, 061304 (2014).

  The prior arts (Patent Documents 1 and 2) perform coating regardless of the surface material of the processing chamber. However, as a result of investigations by the inventors, there are a surface to which a coating film is to be attached and a surface to which the coating film is not attached depending on the material of the processing chamber surface, and the processing chamber surface material and coating conditions need to be appropriately considered and selected. It turns out that. The following three items can be listed if other issues are included.

The first problem is that Si-based coating films and C-based coating films are generally less plasma-resistant than processing chamber surface materials and are related to process condition construction due to easy cutting. For example, CH _x F _y and SiO _x deposited by coating are quartz, SUS (stainless steel), Y used as a processing chamber surface material in plasma containing O (oxygen), F (fluorine), and Cl (chlorine) radicals. (Yttrium) and can be cut more easily than metals containing Al (aluminum). Therefore, it greatly contributes to radical balance during etching of the product wafer, and the etching characteristics are greatly affected by the coating film. Therefore, when a desired etching shape and etching selection ratio are to be realized, if a coating film is deposited in the entire processing chamber, volatile substances (Si, C, H, F, etc.) from the coating film and their reaction products are generated. There is a high possibility that the process window becomes narrow due to the supply of goods.

  The second problem is a process variation caused by the surface temperature of the processing chamber. It is well known that radical balance changes and process fluctuations occur if the surface temperature of the processing chamber is not constant during mass production processing. And control of the process chamber outermost surface temperature is one of the very difficult subjects in the etching apparatus industry. In connection with the first reason, there is a possibility that the process fluctuation range may be further expanded with respect to the temperature change because the etching rate is higher in the coating film than in the processing chamber surface.

  The third problem is that by depositing the coat film on the surface of the processing chamber which is not necessary, the risk of foreign matter generation due to the coat film itself is increased. It is desirable to deposit the coat film on the minimum required surface of the processing chamber.

  The present invention has been made paying attention to these problems, and it is an object of the present invention to provide a plasma processing method capable of reducing foreign substances caused by a processing chamber surface member.

As an embodiment for achieving the above object, a processing chamber in which a first material region containing Si and O and a second material region containing a hardly volatile material are arranged on the surface, and inside the processing chamber In a plasma processing method using a plasma processing apparatus having a gas introducing means for introducing a gas and a plasma generating means for converting the gas into a plasma,
A first step of selectively depositing a CH _x F _y film in the second material region with respect to the first material region of the processing chamber;
Thereafter, a second step of plasma processing the object to be processed disposed inside the processing chamber;
A plasma processing method characterized by comprising:

In addition, in a plasma processing method using a plasma processing apparatus including a processing chamber for processing an object to be processed with plasma, including a quartz inner cylinder and a shower plate, and an earth part,
C and F or C and H introduced into the processing chamber under the condition that the relationship between the surface temperature t ₁ of the inner cylinder and the shower plate and the surface temperature t ₂ of the ground portion is t ₁ > t ₂ First, a CH _x F _y film is coated on the ground portion using a plasma of a gas containing C, H, and F, and a selective coating process is performed in which the CH _x F _y film is not deposited on the inner cylinder and the shower plate. Process,
Then, the plasma processing method includes a second step of performing a plasma etching process on the object to be processed.

  According to the present invention, it is possible to provide a plasma processing method capable of reducing foreign substances caused by a processing chamber surface member.

It is a longitudinal cross-sectional view which shows an example of the plasma processing apparatus (microwave ECR etching apparatus) for enforcing the plasma processing method based on the 1st Example of this invention. It is a processing flowchart for demonstrating the plasma processing method which concerns on each Example of this invention. FIG. 1 is a schematic view showing a reaction between a processing chamber surface material (a hardly volatile material such as Y ₂ O ₃ , YF _{3, and} SUS) and radicals in the plasma when CHF ₃ plasma is generated inside the processing chamber of the plasma processing apparatus shown in FIG. FIG. FIG. 2 is a schematic diagram showing a reaction between a processing chamber surface material (quartz material) and radicals in the plasma when CHF ₃ plasma is generated inside the processing chamber of the plasma processing apparatus shown in FIG. 1. It is an aptitude table of gas conditions in which CHxFy is deposited on the hardly volatile member and is not deposited on the quartz member. It is a graph which shows a dimension trend when 25 lots of 1 lot of hard mask processing (product etching) with a target dimension of 16 nm is processed using the plasma processing method according to each embodiment of the present invention. Is a graph showing the CH _x F _y coated foreign matter the change in the number of non-volatile material composition in the presence and absence of the non-volatile member. It is a processing flowchart for demonstrating the plasma processing method which concerns on the 3rd and 4th Example of this invention.

  Hereinafter, the present invention will be described with reference to examples.

  A plasma processing method according to a first embodiment of the present invention will be described with reference to the drawings. As an example of an etching apparatus to which the present plasma processing method is applied, a microwave ECR etching apparatus shown in FIG. 1 can be used. This etching apparatus includes an electrode 111 for placing a wafer (object to be processed) 110 inside a processing container 120, a gas supply device 132, a top plate 140, a quartz shower plate 101, a quartz inner cylinder 102, It has a grounded earth 103 made of a hardly volatile material, an electromagnet 142, a high-frequency power source 150 for generating plasma, an RF bias power source 161, a matching unit 162, and a vacuum exhaust valve 171 for the processing chamber. .

A plasma processing method according to the present embodiment will be described with reference to FIG. 2 based on the apparatus configuration shown in FIG. FIG. 2 is a process flow diagram for explaining a plasma processing method according to each embodiment of the present invention. The first embodiment includes a first step S210 for performing a CH _x F _y coating process and a second step S220 for performing a product wafer etching process in the etching flow shown in FIG.

In the first step S210, the CH _x F _y film is deposited on a grounded earth composed of a hardly volatile material among the processing chamber surface materials, while the quartz shower plate 101 and the like are included in the processing chamber surface materials. Plasma treatment is performed so that a CH _x F _y film is not deposited on the surface of a quartz treatment chamber such as the quartz inner cylinder 102. The inventors have found that this deposition difference can be realized by appropriately selecting the processing chamber surface material and the gas used for the plasma. That is, it was confirmed that CH _x F _y was deposited on the hardly volatile material, and that no CH _x F _y film was deposited on the quartz surface (this phenomenon will be referred to as a selection deposit in the future). An example of this mechanism will be described below with reference to FIGS. 3A and 3B.

3A and 3B are schematic views showing the reaction between each processing chamber surface material and radicals in the plasma when CHF ₃ plasma is generated inside the processing chamber of the plasma processing apparatus shown in FIG. 3A is a schematic diagram showing a reaction mechanism when a hardly volatile material (Y ₂ O ₃ , YF ₃ , SUS) is used as a processing chamber surface material, and FIG. 3B is a reaction mechanism when a quartz material is used as the processing chamber surface material. It is.

It is known that a hardly volatile material becomes a non-volatile substance such as YF _x or CrF _x even if Y compound or SUS reacts with F, and the etching rate is very slow. Therefore, as shown in FIG. 3A, the CH _x F _y film easily adheres to the surface of the hardly volatile material from the start of coating, and the CH _x F _y film grows as the processing time increases. The growth rate of this film may be considered linear with respect to the plasma processing time.

On the other hand, as shown in FIG. 3B, it is estimated that a reaction such as SiO ₂ + 2CHF ₃ → SiF ₄ + 2CO + 2HF occurs in the quartz material. As a result, most of the C deposited on the nonvolatile material is volatilized as CO. Furthermore, even if a small amount of C is deposited, the remaining HF is further chemically adsorbed on the quartz surface and etched. For this reason, C on the quartz surface is easily lifted off, and the CH _x F _y film does not adhere.

In addition, we investigated etching gases that allow such selective deposition in various gas systems. FIG. 4 is an aptitude table of gas conditions in which CH _x F _y is deposited on the hardly volatile member but not on the quartz member. CF ₄ is not suitable because it is not deposited with both materials (hardly volatile member, quartz member). On the other hand, C ₄ F ₆ , C ₄ F ₈ , and CH ₃ F gas, which are known to have strong deposition properties, are not suitable because they are deposited on quartz.

However, it has been found that selective deposition can be made possible by adding H ₂ and O ₂ gas or N ₂ to C ₄ F ₈ gas. This is presumably because the addition of O ₂ or N ₂ has the effect of weakening the C depotability. That is, it is considered that C + O → CO and C + N → CN are volatilized, increasing the F in the C / F ratio, and promoting the generation of HF by adding H ₂ , thereby preventing deposition from depositing on quartz.

Further, from this reason, it was confirmed that selective depot can be realized even if H ₂ and SF ₆ gas or CF ₄ gas is added to C ₄ F ₈ gas. Moreover, since S reacts with C to become CS, the amount of C can be controlled.

Furthermore, it was confirmed that selective deposition can be realized by adding H ₂ to CF ₄ gas having a weak deposition property. This is considered to be because HF promoted the etching of quartz as the C / F ratio decreased due to H + F → HF.

  From these facts, in order to realize the selective depot, the appropriate C / F ratio control is performed, and the presence of C as the source of the depot and the presence of HF that promotes the etching of the quartz surface are key. all right. Therefore, it has been found that a selection depot can be realized when HF is generated.

As described above, in the first step S210 of this embodiment, the CH _x F _y film is selectively deposited on the quartz material on the surface of the processing chamber made of the hardly volatile material. Next, in a second step, the product wafer is etched. Thereby, in the 2nd process S220, since a shaving and corrosion of a hardly volatile material can be controlled in principle, a foreign substance derived from a processing chamber surface member (earth 103) which is a hardly volatile substance can be reduced. Further, there is no deposition of CH _x F _y on the quartz material, material fluctuation on the surface of the processing chamber due to peeling of CH _x F _{y and} the like is suppressed, the temperature on the surface of the processing chamber becomes constant, process fluctuation is reduced, Stable mass production processing can be performed.

In the product etching (second step S220), only one wafer may be processed, or a plurality of sheets may be continuously processed as in one lot (25 sheets). That is, the processing time of the first step S210 for performing the CH _x F _y coating process according to the number of processed sheets is adjusted, and the coating of the CH _x F _y film on the surface of the processing chamber made of a hardly volatile material is not removed. It is because it is possible to adjust as follows. Further, in this embodiment, the quartz material such as the quartz shower plate 101 and the quartz inner cylinder 102 has been described as an example of the processing chamber surface material. However, if the surface material contains Si and O, CH _x F _y is used. Selection depots can be realized.

Finally, the relationship between the surface temperature t _{1 of the} material containing Si and O, such as the quartz shower plate 101 and the quartz inner cylinder 102, and the surface temperature t ₂ of the grounded earth 103 composed of the hardly volatile material is t ₁ > it is desirable to increase the difference in t ₁ and t ₂ and at t _2. This application makes it possible to make the selection depot more prominent. That is, CH _x F _y is not deposited on materials containing Si and O such as the quartz shower plate 101 and the quartz inner cylinder 102, whereas the grounded earth 103 made of a hardly volatile material has a high rate. As a result, CH _x F _y is deposited.

As described above, according to the present embodiment, it is possible to provide a plasma processing method capable of reducing foreign substances caused by the processing chamber surface member. Further, the CH _x F _y film is selectively deposited and there is no CH _x F _y deposition on the quartz material, and the process chamber surface temperature can be kept constant, thereby reducing process fluctuations and performing stable mass production processing. Can do.

A plasma processing method according to the second embodiment of the present invention will be described. Note that the matters described in the first embodiment and not described in the present embodiment can also be applied to the present embodiment unless there are special circumstances. In the first embodiment, the processing method including the first step S210 for performing the CH _x F _y coating process and the second step S220 for performing the product etching process in the etching flow shown in FIG. 2 has been described. In the second embodiment, in addition to the first and second steps in the etching flow shown in FIG. 2, a seasoning process S310 for adjusting the surface state of the quartz member is included between the first and second steps.

  The seasoning process S310 is performed before the process chamber is transferred to the product wafer before the product etching (second step S210). A dummy wafer may be used or waferless. The seasoning process is a process performed mainly for adjusting the state of the outermost surface of 1 to 2 nm of the quartz member and realizing the same surface state as during product etching.

  FIG. 5 is a graph showing a dimensional trend when 25 lots of 1 lot of hard mask processing (product etching) with a target dimension of 16 nm are processed. The presence or absence of seasoning is indicated by different plots. In the case where the seasoning process is not performed, the 1st wafer effect in which the size is particularly reduced is seen in the first sheet, while the 1st wafer effect is improved with the seasoning process. In this embodiment, the seasoning process plasma conditions are exactly the same as the product etching process conditions, but the same is true even if some of them are the same (for example, the last few recipes if they are composed of multiple recipes). May be expected.

  As described above, since the state of the outermost surface of 1 to 2 nm of the quartz member can be adjusted by performing the seasoning process S310 of the present embodiment, a more stable mass production process can be performed as compared with the first embodiment.

  As described above, according to the present embodiment, the same effects as those of the first embodiment can be obtained. Further, by performing the seasoning process, a more stable mass production process can be performed as compared to the first embodiment.

A plasma processing method according to the third embodiment of the present invention will be described. Note that matters described in the first or second embodiment but not described in the present embodiment can also be applied to the present embodiment unless there are special circumstances. In the first embodiment, the processing method including the first step S210 for performing the CH _x F _y coating process and the second step S220 for performing the product etching process in the etching flow shown in FIG. 2 has been described. In the third embodiment, in addition to the first and second steps in the etching flow shown in FIG. 2, a step of cleaning the reaction product produced by etching the product wafer and deposited on the surface of the processing chamber (metal) (Cleaning process step) S410 and a step S420 for cleaning the CH _x F _y deposit on the ground 103.

Al (AlO, AlF) and Ti (TiF, TiO) are well known as hardly volatile reaction products. In the case where these metals are deposited on the surface of the processing chamber in the second step S220, subsequent mass production processing may cause process variations. Therefore, proper metal cleaning must be performed. As the gas used in the metal cleaning process step S410, a gas containing BCl ₃ , SiCl ₄ , HCl, a mixed gas of these gases and Cl _2, a mixed gas containing C and Cl, or a mixed gas containing H and Cl is effective. . This is due to the fact that Al and Ti are highly volatile in chloride, and it is necessary to promote chlorination. That is, inclusions other than Cl are expected to function as a reducing agent for promoting chlorination.

Next, the CH _x F _y film in the ground portion may or may not be removed after the second step. If the removal is insufficient, the CH _x F _y film may continue to grow by performing mass production processing, and this film may peel off and become a foreign substance. Therefore, cleaning of the CH _x F _y film is effective. As the gas used in the CH _x F _y cleaning processing step S420, a gas containing O or N effective for removing the CHxFy film in the ground portion is suitable, and when Si is contained during the etching of the product wafer. A gas containing SF ₆ , CF ₄ , or NF ₃ which is an effective F-based gas for the Si-based reaction product is used, or a mixed gas containing O or N is optimal.

In the sequence shown in FIG. 2, the first process S210, the seasoning process S310, the second process S220, the metal cleaning process S410, and the CH _x F _y cleaning process S420 are performed in the order of the first process S210. A continuous treatment was performed depending on the presence or absence of the treatment, and the transition of the number of foreign matters having a particle size of 30 nm or more was examined using a Review SEM. FIG. 6 is a graph showing the transition of the number of foreign substances of the non-volatile substance composition with and without the CH _x F _y coating treatment. In the absence of the CH _x F _y coating treatment, about 10 foreign matters were observed, while in the presence of the CH _x F _y coating treatment, no foreign matter was observed and very good results were obtained.

From the above, it was confirmed that the foreign matter adhesion can be suppressed by the CH _x F _y coating treatment in the first step (the number of foreign matters with treatment is smaller than that without treatment). Further, by using the metal cleaning processing step S410 and the CH _x F _y cleaning processing step S420 newly added to the first step in the first step, the generation of a hardly volatile reaction on the surface of the processing chamber generated in the second step. It can be seen that the objects are also removed (the number of attached different parts is not observed). Therefore, by performing the metal cleaning process and the CH _x F _y cleaning process, it is possible to suppress process fluctuations in the mass production process over a longer period than in the first embodiment. In addition, since the generation of foreign matter due to an extreme increase in the deposited film of the CH _x F _y film on the earth 103 can be suppressed, more stable mass production processing can be performed. In product etching in actual mass production, the product (wafer) can be taken out from the processing chamber between the second step and the metal cleaning processing step S410. Further, the product (wafer) can be taken out from the processing chamber between the metal cleaning processing step S410 and the CH _x F _y cleaning processing step S420.

The main factor that damages the grounded earth 103 made of a hardly volatile material may be a metal cleaning process (step S410) in the sequence of FIG. In this case, the sequence shown in FIG. 7 can be used. FIG. 7 is another process flow chart for explaining the plasma processing method according to the present embodiment, and mass production etching for performing a metal cleaning process (process S411) after the CH _x F _y coating (first process S210). It is a flow. In this case, no foreign matter is generated as long as the CH _x F _y film of the grounding portion that is grounded only during metal cleaning is coated. On the other hand, the hardly volatile reaction product on the quartz surface can be easily removed.

As described above, according to the present embodiment, the same effects as those of the first embodiment can be obtained. Further, the number of adhered foreign matters can be further reduced by using the metal cleaning process (steps S410 and S411) and the CH _x F _y film cleaning process (step S420).

A plasma processing method according to the fourth embodiment of the present invention will be described. Note that the matters described in any of the first to third embodiments but not described in the present embodiment can also be applied to the present embodiment unless there are special circumstances. In the first embodiment, the processing method including the first step S210 for performing the CH _x F _y coating process and the second step S220 for performing the product etching process in the etching flow shown in FIG. 2 has been described. The fourth embodiment includes a step S510 of performing a heating process for increasing the processing chamber surface temperature before the first and second steps in the etching flow shown in FIG.

But it is possible to suppress the deposition of CH _x F _y to the first step S210 only the selected depot CH _x F _y in is possible and quartz surface shown in the first embodiment, the temperature of the processing chamber surfaces By controlling the above, it is possible to reduce the adhesion at the ultra-thin nm level to the quartz surface to the limit, and the selectivity is improved. In addition to the effect of reducing the CH _x F _y deposit adhesion coefficient on the quartz surface, this can be expected to increase the reaction rate due to chemical adsorption of HF, that is, to increase the etching rate of quartz, thereby further increasing the C lift-off effect. Therefore, a deposition process on the quartz surface is performed by performing a heating process (process S510) for increasing the surface temperature of the processing chamber using plasma before the first process S210, and then performing the first process S210. Can be reduced to the limit. The gas used for the heating process (step S510) is preferably a gas containing Ar, He, O, or F that does not affect the surface state of the processing chamber or has a Si or C cleaning effect.

As described above, the CH _x F _y deposit adhesion on the quartz surface can be reduced to the minimum by performing the heating processing step S510 of the present embodiment. For this reason, it becomes possible to make the effect of Example 1 more remarkable, and mass production processing can be performed stably.

As described above, according to the present embodiment, the same effects as those of the first embodiment can be obtained. Further, by performing the heating process before the CH _x F _y coating process, the selectivity during the CH _x F _y coating is improved as compared with the first embodiment.

  In addition, this invention is not limited to an above-described Example, Various modifications are included. For example, the above-described embodiments have been described in detail for easy understanding of the present invention, and are not necessarily limited to those having all the configurations described. Further, a part of the configuration of a certain embodiment can be replaced with the configuration of another embodiment, and the configuration of another embodiment can be added to the configuration of a certain embodiment. Further, it is possible to add, delete, and replace other configurations for a part of the configuration of each embodiment.

DESCRIPTION OF SYMBOLS 101: Quartz shower plate, 102: Quartz inner cylinder, 103: Grounding earth | ground comprised with a hardly volatile material, 110: Wafer (to-be-processed object), 111: Electrode, 132: Gas supply apparatus, 140: Sky Plate: 142: Electromagnet, 150: High-frequency power source for generating plasma, 161: RF bias power source, 162: Matching unit, 171: Vacuum exhaust valve of the processing chamber, S210: CH _x F _y coating processing step (first step) , S220: Product wafer etching process (second process), S310: Seasoning process for adjusting the surface state of the quartz member, S410: Reaction product cleaning process generated by etching the product wafer, S420: Earth cleaning process of the _CH x _{F y} deposits parts, S510: heating increases the processing chamber surface temperature computing Management process.

Claims (8)

In a plasma processing method of performing plasma processing on an object to be processed in a processing chamber using a first material containing Si element and O element and a second material which is a hardly volatile material as a surface material ,
A first step of selectively depositing a film containing a C element, an H element, and an F element on the surface of the processing chamber constituted by the second material with respect to the surface of the processing chamber constituted by the first material. When,
And a second step of plasma-treating the object to be treated after the first step. The plasma processing method according to claim 1,
The plasma processing method is characterized in that the first step deposits a film containing the C element, the H element, and the F element by using plasma with a gas containing a C element, an H element, and an F element. The plasma processing method according to claim 2,
The gas is CHF ₃ gas, mixed gas of CHF ₃ gas and O ₂ gas, mixed gas of CF ₄ gas and H ₂ gas, mixed gas of C ₄ F ₈ gas, H ₂ gas and O ₂ gas, C ₄ F _{It is} a mixed gas of ₈ gas, H ₂ gas and N ₂ gas, a mixed gas of C ₄ F ₈ gas, H ₂ gas and SF ₆ gas or a mixed gas of C ₄ F ₈ gas, H ₂ gas and CF ₄ gas A plasma processing method characterized by the above. In the plasma processing method according to any one of claims 1 to 3,
The plasma processing method, wherein the second material is stainless steel (SUS) or a material containing an yttrium (Y) element or an aluminum (Al) element. In the plasma processing method according to any one of claims 1 to 4,
The first step is a plasma processing method characterized in that the temperature of the first configured processing chamber surface of a material is performed when the temperature is greater than the second configured processing chamber surfaces by material . In the plasma processing method as described in any one of Claims 1 thru | or 5,
The plasma processing method characterized by performing the heating process which raises the temperature of the process chamber surface comprised with the said 1st material before the said 1st process. In the plasma processing method according to any one of claims 1 to 6,
A plasma processing method, wherein a seasoning step for performing the same plasma processing as part or all of the plasma processing in the second step is performed between the first step and the second step. In the plasma processing method as described in any one of Claims 1 thru | or 7,
A metal cleaning step for removing a reaction product of a metal deposited in the processing chamber when a film containing the C element, H element, and F element is deposited on the surface of the processing chamber constituted by the second material. Is performed between the first step and the second step.

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