TW200301311A - Method for processing substrates - Google Patents

Abstract

The method for processing substrates according to this invention comprises a step of oxidizing the surface of the silicon substrate for forming an oxide film, and a step of nitrifying the oxide film for forming an oxy-nitride film, and further comprises a step of exhausting oxygen of the surrounding in which the oxide film is nitrified between steps of oxidization and nitrification.

Description

200301311 V. Description of the invention (1) 1. [Technical field to which the invention belongs] The present invention relates to general substrate processing technology, and particularly relates to a substrate processing method for forming a high dielectric film on a substrate. With the progress of miniaturization technology, it is now possible to manufacture ultra-finely-processed semiconductor devices with MOS transistors with a gate length of less than 0.1 m. 6 In this ultra-fine-processed semiconductor device, in order to shorten the gate of M0S transistors In order to increase the pole length and increase the operating speed of a semiconductor device, it is necessary to reduce the thickness of the gate insulating film according to the law of proportionality. For example, if a conventional silicon oxide film is used as the gate insulating film, the thickness of the gate insulating film must be reduced to a conventional value of 1 · 7nm or less. However, if the thickness of the oxide film is reduced to this extent, the gate leakage current flowing through the oxide film will increase due to the tunnel effect, resulting in deterioration of device characteristics such as increased power consumption. Therefore, it has been reviewed from the past to replace traditional silicon oxide films with high dielectric films such as Ta205, Zr02, Hf02, or A1203. However, in terms of semiconductor technology, the properties of these high-dielectric films are quite different from those of traditionally used silicon oxide films. In order to apply these high-dielectric films as gate insulating films, there are still many problems to be solved. In contrast, the silicon nitride film is a material that has been used in traditional semiconductor processing, and has a dielectric constant that is twice that of the silicon oxide film, and can effectively prevent the doping elements in the gate from diffusing to the silicon substrate, so it is very useful. It may be a material for a gate insulating film of a next-generation high-speed semiconductor device. 2. [Previous Technology] Traditionally, a plasma CVD method is generally used to form a silicon nitride film. However, in general, such CVD nitride films are not suitable due to poor interface characteristics.

200301311 V. Description of the invention (2) Used as gate insulation film. Therefore, no attempt has been made to apply a conventional nitride film to the gate insulating film. In contrast, recently, it has been proposed to introduce a nitrogen-containing gas such as nitrogen, nitrogen and hydrogen, or NH3 into a rare gas plasma such as microwave-excited Ar, Kr, or He to generate N free radicals or ions. Free radicals, a technology that transforms the surface of a silicon oxide film into a nitrogen oxide film (Kasuyuki Sekine,

Yu ji Sato, Masaki Hirayama and Tadahiro ohmi, J. Vac · Sci · Technol · A17 (5), Sept / Oct 1999, pp, 3 1 29- 3 1 33; Takuya Sugawara, Toshio Nakanishi, Masaru Sasaki, Shigenori Ozaki, Yoshihide Tade, Extended Abstracts of Solid State Devices and Materials, 2002, pp.714-715). The nitrogen oxide film formed in this way has the same or better interface characteristics as the silicon thermal oxide film, and is likely to become the gate insulating film of the next-generation high-speed semiconductor device. In addition, some people have proposed a plasma nitridation technique for directly performing nitriding on the surface of a silicon substrate using this microwave plasma, and a plasma oxidation technique for directly introducing an oxygen-containing gas into the aforementioned rare gas plasma and performing oxidation. … In addition, when the plasma nitridation treatment is performed after the oxidation treatment on the surface of the Shixi substrate in the same device, if the oxygen introduced during the oxidation treatment or other treatments remains in the processing environment, the nitridation treatment will also be oxidized at the same time. As a result, there is a problem that the film thickness of the gate insulating film formed by the nitriding process increases. On the right, the phenomenon that the film thickness of the gate insulating film is increased, it is impossible to obtain the desired increase in the operating speed of the semiconductor device according to the law of proportionality. In order to increase the thickness of the gate insulating film,

Page 7 200301311 V. Description of the invention (3) = 1 When full diffusion is performed in the direction of long-term nitriding, or oxygen at the bottom layer: it is particularly obvious when the film is thin (Takuya Sugawara, et al., Op. Cit., cc Chen, MC Yu, MF Wang, TL Lee, C, Chen? C, H · Yu and MS Liang, 2 0 0 2 7 th international Symposium on Plasma and Process' I nduced D amage, pp · 4 i a 4 4 ). #If oxidation treatment and nitridation treatment are implemented in different devices, the moisture absorbed when the substrate * oxidation treatment is moved into the nitridation treatment device will also increase the film thickness of the interlayer insulating film due to oxidation. Same problem. 3. [DISCLOSURE OF THE INVENTION] Therefore, the subject of the present invention is to provide a new and effective substrate processing apparatus and processing method capable of solving the aforementioned problems. A more specific problem of the present invention is to provide a substrate processing method and a substrate fetching device. After the oxidation treatment of the surface of the stone substrate, the substrate is subjected to a counter treatment. When the oxide film is subjected to the nitriding treatment, it can suppress the nitriding. The thickness of the nitrogen-rolled film formed by the treatment increases. Another subject of the present invention is to provide a substrate processing method, comprising: a step of forming an oxide film by performing an oxidation treatment on a surface of a silicon substrate; and a step of forming a oxynitride film by performing a nitridation treatment on a silicon oxide film; and After the second oxidation treatment step and before the nitriding treatment step, a step of removing oxygen from the environment where the nitriding treatment is performed is included.

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V. Description of the invention (4) ___ According to the present invention, when the surface of the silicon substrate is formed, the thickness of the nitrogen film remaining in the processing environment can be inhibited from being nitrided and thickened: it is suitable for ultra-high speed half; = Film 溥 Nitrogen oxide film. n. The poles of the lamina membrane. [Embodiment] A preferred embodiment of the present invention is as follows. [苐 1 实施 例]. FIG. 1 is a schematic diagram of a plasma substrate processing apparatus 10 used in the present invention. FIG. 1 shows a plasma substrate processing apparatus 10 having a processing container 11 forming a fixing plate fixing table 12 and a processing container 11; Crying beautiful; / In: Ding exhaust. In the aforementioned substrate fixing table 12, a substrate temperature control mechanism 12a is formed. Then, the processing container 11 will correspond to the opening on the substrate fixing table 12: = the substrate W to form an opening, and the opening is sealed by a cymbal plate 13 made of low consumption ceramic such as alumina. Below the cover plate 13 is a diffuser plate 14 composed of a low-consumption ceramic magnet such as alumina, which forms a gas introduction path and a plurality of nozzle openings communicating with the substrate W facing the substrate W to be treated. For example, the cover plate 13 and the diffuser plate 14 will form a microwave window, and on the outer side of the cover plate 1 3, a radiation antenna 15 or a microwave antenna 15 such as a slot antenna or a stub antenna will be formed.

During operation, the processing space inside the processing container 11 will be exhausted through the exhaust port 1 1 A to be under a specific processing pressure. Then, the diffuser plate 14 will simultaneously introduce rare gases such as Ar or Kr, And oxidizing gas or

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li

Tritium gas. Note: The upper part of the line 15 is irradiated with a microwave having a frequency of several GHz. Zhao ’s microwave will be transmitted in the diameter direction of the antenna and emitted toward the lower part of the antenna. ",,,, & cover plate U is introduced into the vacuum container n. At this time, I passes through the antenna: ^ waves, so high density will be generated. The uniform distribution of low electron temperature. In this case, the electron temperature of the plasma in the substrate processing device of Fig. 1 will be lower, which can avoid damage to the substrate w and the processing container.

Also, 'the formed radicals will flow in the diameter direction along the surface of the substrate to be processed, and the rapid re-exhaustion is performed, so the recombination of radicals can be inhibited', and the efficiency can be applied under the low service of 6 0 C Good and consistent substrate processing. FIG. 2 shows the use of the substrate processing device 1 in FIG. 1 to perform an oxidation treatment on the surface of the Shixi substrate, and then to perform a nitridation treatment on the obtained plasma oxide film to form an oxynitride film. SIMS (Secondary Ion Mass Spectrometer) diagram. However, the experiment in FIG. 2 is to provide Ar gas and oxygen to the processing container 11 of the substrate processing apparatus 10 in the aforementioned FIG. 1 at a flow rate of 1,000 CCM and 20 SCCM, respectively, at a level of ΙββχΙί ^ Α. Under the pressure and substrate temperature of 40 ° C, a microwave of 45 GHz is provided with a power of 15 0 W to form an oxide film with a thickness of about 6 nm. In the implementation of nitriding, the flow is 100 SCCM and 20 SCCM respectively. Provide Ar gas and oxygen. Under the pressure of USxliTPa and the substrate temperature of 40 ° C, the microwave of 45GHz is provided with the power of 150W. Referring to FIG. 2, it can be seen that, in the form of a concentrated region near the surface of the oxide film, nitrogen atoms diffuse from the nitrogen-concentrated region to the inside of the oxide film. The nitrogen oxide film formed by the diffusion of nitrogen atoms into the oxide film ’

Page 10 200301311 V. Description of the invention (6) No interface will be formed between the region and the oxide film, so no trap will be formed in the film. In Figure 2, there are still nitrogen and oxygen concentration distributions when the nitriding time is changed. From Figure 2, it can be seen that the longer the nitriding time, the higher the oxygen concentration in the film will be. Oxygen can penetrate the inside of the silicon substrate and increase the thickness of the oxide film. The oxygen that causes such an increase in the thickness of the oxide film should come from oxygen molecules attached to the inner wall of the processing vessel 11 or the gas supply pipe, or moisture attached to the surface of the substrate. FIGS. 3A to 3C show the mechanism for generating such an oxide film thickness when performing the nitriding treatment during oxidation and nitridation in the substrate processing apparatus 10 of the aforementioned FIG. 1 and a mechanism capable of suppressing such an oxide film thickness. A substrate processing method according to a first embodiment of the invention. FIG. 3A shows the plasma irradiation sequence in the processing container 11 during the oxidation treatment and nitridation treatment, FIG. 3B shows the oxygen concentration change in the processing container 11 described above, and FIG. 3C shows the processing container 11 described above. The nitrogen concentration changes. Referring to FIG. 3A, during the above-mentioned oxidation treatment and nitridation treatment, A r plasma A and B will be excited in the processing container 11 respectively, and in the manner of FIG. 3B during the oxidation treatment, Oxygen is introduced into the processing container 11, and nitrogen is introduced into the processing container 11 in the manner shown in FIG. 3C during nitriding. When the oxidation treatment is completed, the plasma A is turned off and the oxygen supply is stopped. Similarly, when the nitriding process is completed, the plasma B that was originally irradiated is turned off, and the nitrogen supply is stopped. Especially at the timing of ending the oxidation process, although the supply of oxygen has been stopped, the oxygen molecules attached to the wall of the processing vessel or the gas supply pipeline will be slowly released, so as shown in FIG. 3B, the aforementioned processing vessel 11 Oxygen concentration

Page 11 200301311 V. Description of the invention (7) The tail will appear on the picture. As a result of the chemical treatment of the physical container 1 i, after the electric power at the time of the beam of nitrogen, V, and ° indicated by the nitrided film V, the processing capacity of the ribs can be used to use the nitrogen in the oxygen physical container 11 to Therefore, when the above-mentioned oxide body is shortened, or when the nitrogen and oxygen are introduced immediately after stopping the oxygen supply and the plasma is irradiated, the oxygen remaining in the processing container 11 will be oxidized on the silicon substrate caused by the oxygen free radicals, Will occur simultaneously with oxygen. In order to solve this problem, the method in FIG. 3A is adopted in this embodiment. The plasma irradiation during nitriding treatment is delayed by 1 to 600 seconds compared with the closing of the oxidation treatment slurry, and the supply of nitrogen and Ar gas is stopped when the oxygen supply is stopped. At the same time, they are introduced into the processing container 11. As a result, the inside of the device 11 was cleaned by the Ar gas and nitrogen gas introduced in the period until the plasma re-irradiation was performed. In this way, the aforementioned processing container 11 after the chemical treatment is cleaned, and the oxygen in the aforementioned part will be quickly eliminated as shown by the dotted line in FIG. 3B, and the substrate processing time will be eliminated. In the foregoing cleaning step, for example, Ar gas may be provided at the same 100% SCCM flow rate as the treatment or nitridation treatment, and nitrogen gas may be provided at the 20 SCCM flow rate. The following Table 1 is a representative formulation example of this embodiment.

11

Table 1

Ar (SCCM) 02CSCCM) N2CSCCM) Microwave power (W) Time (seconds) 1000 20 1500 40 1000 20 0 N2 cleaning 1000 20 1500 30 Page 12 200301311 V. Description of the invention (8) Again, as shown in Figure 3D It can also supply nitrogen intermittently during the cleaning period, that is, implement periodic cleaning. This periodic cleaning can further shorten the cleaning time. Of course, as shown in Fig. 3E, if there is a sufficient time interval between the aforementioned oxidation treatment A and nitridation treatment B, the nitrogen purge may be omitted. [Second Embodiment] FIGS. 4A to 4C are substrate processing methods according to the second embodiment of the present invention using the substrate processing apparatus 10 of FIG. In this embodiment, as shown in FIG. 4A, the plasma is continuously formed from the oxidation treatment step A to the nitridation treatment step B. On the other hand, in this embodiment, in order to prevent the oxide film from being thickened in the nitriding treatment step B, as shown in Fig. 4B, the oxygen supply time t is set to be shorter than the period of the oxidation treatment step. In this way, the oxygen supply step is completed before the end of the oxidation treatment step, and the remaining oxidation treatment step is performed using oxygen remaining in the processing vessel 11 or the gas supply system. In this embodiment, the oxidation treatment has been completed at the point of introduction of nitrogen gas as shown in Fig. 4C. As a result, there is no phenomenon that the oxide film is thickened during the nitridation treatment. In this embodiment, the plasma is continuously formed from the start of the oxidation treatment step to the end of the nitridation treatment step, and the supply of oxygen is stopped in FIG. 4B

Page 13 cU〇03〇131i V. Description of the invention (9) J, the residual oxygen will be consumed by the oxidation treatment, and the residual oxygen concentration will be quickly reduced. Therefore, after the emulsification processing step, the ratification processing step can be started without setting a longer oxygen cleaning step, and the yield of substrate processing can be improved. —And 'as shown in Figure 4D' and the principle of this example. For example, if the electro-stimulation irradiation is stopped immediately after the emulsification step A, and only red plasma irradiation is performed again, then N2 gas is introduced for implementation. Method of nitriding treatment. [Third Embodiment] FIG. 5 is a configuration diagram of a cluster-type substrate processing apparatus 20 according to a third embodiment of the present invention. Referring to FIG. 5, the cluster type substrate processing apparatus 20 includes a vacuum processing chamber 21 connected to the cassette module 2A. The vacuum processing chamber 21 is connected to a substrate processing chamber having the same configuration as that of the substrate processing 1 in the first drawing. 218, 2id, and the pre-processing chamber 21G ° The Shixi substrate placed on the aforementioned cassette module 21A will be transferred to the front-substrate processing by the automatic transfer machine (not shown in the figure) in the aforementioned vacuum transfer chamber 2 丨. The chamber 2 1 B ′ performs a plasma free oxidation treatment in the substrate processing chamber 2] B to form an oxide film on the surface of the silicon substrate. The silicon substrate that has undergone the oxidation treatment using this square-π method is transferred to a pre-processing chamber 2.1C ′ in an Ar or nitrogen environment and stored at 300-600 (). (: A few minutes at the temperature, remove the oxygen molecules adsorbed on the surface of the substrate. The freshly processed Shixi substrate is transferred to the substrate through the vacuum transfer chamber 21 to the substrate processing to 2 1 D '. The same nitriding as described above is performed. At this time, because the substrate processing chamber 2 1D described in 1T does not change the environment, the nitridation process can be started immediately after the substrate is transferred, so the overall substrate processing yield can be improved. Moreover, this implementation

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20000i3U 5. Description of the invention (10) In the example, "the oxygen molecules attached to the substrate to be processed are implemented in the dedicated processing chamber 2 1 C", in addition to improving the removal efficiency, it can also effectively inhibit the nitriding process. Thickening over time. Further, as shown in Fig. 5, since Ar plasma processing is performed in the pre-processing chamber 21C, the pre-processing time of the substrate can be shortened. Such a pretreatment may be performed in the substrate processing chamber 21D. [Fourth embodiment]

Fig. 6 is a block diagram of a cluster-type substrate processing apparatus 30 according to a fourth embodiment of the present invention. Parts previously described in FIG. 6 are denoted by the same symbols, and descriptions thereof are omitted. Referring to Fig. 5, the substrate processing apparatus 30 performs plasma free oxidation treatment in the substrate processing chamber 21B. Specifically, the "first" substrate to be processed is transferred from the cassette module 21A to the substrate processing chamber 21B via the vacuum transfer chamber 21, and the plasma free oxidation treatment described above is performed. The substrate to be processed after the oxidation process is transferred to the pre-processing chamber 2ic through the vacuum transfer chamber 21, and the adsorbed oxygen molecules are removed by heat treatment or Ar plasma treatment.

While the substrate to be processed is being processed in the pre-processing chamber 2 1 C, the substrate processing chamber 2 1 B is as shown in the description of Figs. 3 and 4 A to C above. 'Convert the oxygen environment to nitrogen surroundings. In addition, while the pre-processing chamber 2 1 C is processing the substrate to be processed, a virtual wafer is introduced into the processing chamber 2 1 B, and the plasma of the virtual wafer can be used to convert the environment of the processing chamber 2 1 B into nitrogen. surroundings. Also, without virtual chip

W Μ page 15 200301311 V. Description of the invention αυ implements the same treatment. At the time when the substrate to be processed completed in the aforementioned substrate processing chamber 2 1 C is returned to the aforementioned processing chamber 21B via the aforementioned vacuum transfer chamber 21, the environment of the aforementioned processing chamber 2 1 B has been converted into a nitrogen-oxygen environment, and residual oxygen is also completed Molecular cleaning. Therefore, performing plasma irradiation in the aforementioned pre-processing chamber 2 1 C can nitride the oxide film formed on the surface of the substrate to be processed.

In this embodiment, the step of removing oxygen molecules adsorbed on the substrate being processed in the dedicated pre-processing chamber 2 丨 C can be performed simultaneously with the environmental conversion step of the substrate processing chamber 2 丨 B, so the yield of substrate processing can be improved. In addition, as for the substrate processing apparatus 30 of this embodiment, only one substrate processing apparatus 10 shown in FIG. 1 is required, so that the manufacturing cost of the substrate processing apparatus 30 can be reduced. The structure of FIG. 6 is also very effective in nitriding the substrate with the substrate processing device 10 having the structure shown in FIG. 1 by applying a thermal oxidation film formed using an external oxidation treatment device such as a sub-type. 'That is,' the oxygen oxidation performed by an external oxidation treatment device such as thermal oxidation treatment = the stone slab substrate processed will definitely adsorb moisture in the atmosphere when it is transported in the atmosphere ', if the microwave plasma treatment device shown in FIG. This moisture-adsorbed Shi Xiji = Nitriding process is applied, because the substrate temperature is lower during nitriding process.

The method of filling the knife removes water ', so there is a problem that the oxygen in the water causes the substrate to oxidize. In contrast, in the substrate processing apparatus 30 of FIG. 6, the substrates that have passed through the oxygen, gas, and silicon substrates are directly transferred from the cassette module 2 1 Α to the grate processing chamber 21C as shown by the dotted lines in the figure. In the foregoing pre-processing chamber 21C, 300 to 600 ° C $ i0 · ^^^ <heating treatment or plasma treatment is performed in an Ar environment, so that the absorbed moisture can be 200301311 V. Description of the invention (12) The ions are detached from the surface of the substrate. In this way, the substrate to be processed which has been pre-processed is transferred to the aforementioned substrate processing chamber 2 1 B, and nitridation of the oxide film can be performed without the occurrence of thickening due to oxidation. At this time, since the substrate processing chamber 2 1 B is exclusively used for nitriding treatment, there is no need to switch the ambient gas, and there is no problem of oxidation due to the substrate processing and the residual oxygen in the chamber 2 1 B. If necessary, the functions of the pre-processing chamber 2 1 C may be integrated in the substrate processing chamber 21B.

At this time, the substrate processing device 10 shown in the first figure in the substrate processing chamber 2 1 B will drive the substrate temperature control mechanism in the substrate fixing table 12 2a, and heat the substrate to 3 in the Ar environment. 〇〇 ～ 600 0 ° C。 Temperature. At this time, of course, it is also possible to form an electropolymer according to the needs. ^ The following is a description of a good embodiment of the present invention. However, the present invention is not limited by the foregoing embodiments, as long as it can implement various modifications or changes. The industrial use of the present invention is as follows. According to the present invention, it is possible to suppress the formation of a nitrided film due to the residual :: reverse: surface oxide film during the shape &amp; treatment. Ultra-thin nitrogen of the idler insulating film of the bulk device 200301311 Brief description of the drawings 5. [Simplified description of the drawings] Fig. 1 is a structural diagram of a substrate processing device used in the first embodiment of the present invention. Fig. 2 is a distribution diagram of oxygen atoms and nitrogen atoms in the oxynitride film formed when the silicon substrate is subjected to an oxidation treatment and a nitridation treatment in the substrate processing apparatus of Fig. 1 continuously. Figures 3 to A are explanatory diagrams of a substrate processing method according to the first embodiment of the present invention. Figures 4 to A are explanatory diagrams of a substrate processing method according to a second embodiment of the present invention. Fig. 5 is an explanatory diagram of a substrate processing method using a cluster-type substrate processing apparatus according to a third embodiment of the present invention. Fig. 6 is an explanatory diagram of a substrate processing method using a cluster-type substrate processing apparatus according to a fourth embodiment of the present invention. [Explanation of component symbols] W ~ substrate to be processed 0 ~ plasma substrate processing device I 1 ~ processing container II A ~ exhaust port 1 2 ~ substrate fixing stage 1 2a ~ substrate temperature control mechanism 1 3 ~ cover 1 4 ~ diffuser

P.18 200301311 Brief description of drawings 1 5 ~ Microwave antenna 2 0 ~ Cluster substrate processing device 2 1 ~ Vacuum transfer chamber 2 1 A ~ Card module 21B, 21D ~ Substrate processing chamber 2 1 C ~ Pre-processing chamber #

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Claims (1)

200301311 VI. Application for Patent Scope 1. A substrate processing method, including: a step of forming an oxide film by chemical treatment, a step of forming an oxynitride film by chemical treatment; after the step of the oxidation treatment, the environment of the nitriding treatment excludes oxygen Step 2. If the oxidation treatment is based on item 1 of the scope of the patent application, the oxidation treatment is performed in a batch process, and the method is performed in this manner. 3. If the basis of item 2 of the scope of patent application is applied, the heat treatment is carried out in the application of the gas. 4. If the basis of item 2 of the scope of patent application is applied, the heat treatment is carried out and implemented in the other processing device. 5. As the basis of item 1 of the scope of the patent application, the oxidation treatment is performed in a batch process and the early film treatment method is performed by the 'Lu Hai method. 6. If the base of the scope of patent application No. 5 is applied, the plasma treatment is applied with nitrogen. 7. As the basis of the scope of the patent application No. 5, the plasma treatment is implemented in and implemented in the other processing devices. By applying oxygen to the surface of the silicon substrate and by applying nitrogen to the oxide film, it is further characterized in that: before the nitriding treatment step, the steps are carried out. The plate treatment method is carried out in the method. The step of removing the oxygen is performed by heating. The plate treatment method is performed in a treatment device of the chemical treatment. Plate treatment method, in which the nitriding treatment device is different from the plate treatment method, in which the step of 'the nitrogen i treatment is to exclude oxygen is a plasma treatment plate treatment method, which is implemented in the treatment device of the chemical treatment Plate processing method, in which the nitriding treatment device is different Page 20 200301311 6. Scope of patent application 8. The substrate processing method as described in item 2 of the patent scope, wherein the nitriding treatment is performed by plasma processing. 9. For the substrate processing method according to item 1 of the patent application scope, wherein the oxidation treatment is performed in the first monolithic processing device, the nitridation treatment is performed in the second monolithic processing device, and the oxygen removal The steps are performed by heat treatment and plasma treatment. 10. The substrate processing method according to item 9 of the scope of patent application, wherein the heat treatment and plasma treatment are implemented in the second single-chip processing apparatus. Refer to 11. The substrate processing method according to item 9 of the scope of patent application, wherein the heat treatment and plasma treatment are performed in another processing device different from the second single-chip processing device. 1 2. The substrate processing method according to item 9 of the scope of patent application, wherein the oxidation treatment and nitridation treatment are performed by plasma treatment. 1 3. If the substrate processing method according to item 1 of the patent application scope, wherein the oxidation treatment and nitridation treatment are sequentially performed by plasma treatment in a single single-chip processing device, the step of excluding oxygen is from the oxidation The period from the end of the treated plasma treatment to the start of the nitridation plasma treatment is carried out by continuously performing a step of exhausting gas in the processing container of the single-chip processing apparatus. 14. The substrate processing method according to item 13 of the scope of patent application, wherein the step of removing oxygen is performed while continuously exhausting in the processing container while supplying nitrogen and / or noble gas to the processing container. . 15. For the substrate processing method of item 13 or 14 in the scope of patent application, where Page 21 200301311 Sixth, the scope of the patent application 1 of the single-chip processing device for oxygen exclusion 6. If the patent is applied, the step of step 17 of the treatment container is intermittent, if the patent is applied, the second treatment for oxidation treatment Plasma implementation: Carry out the nitriding treatment 18. If applying for a patent, the oxidation treatment gas and nitrogen will stop the oxygen supply before the beam. 19: If applying for a patent, the plasma system will benefit 20, if applying for a patent, the plasma system will benefit 0 The steps are carried out in a state where the substrate is further transported to the other device. The substrate processing method of the item 13 of the scope, wherein the steps include the steps of: intermittently supplying nitrogen and / or a rare gas to the step during the continuous exhausting step. The substrate processing method in the range of item 13 is implemented by using the first plasma, and the nitriding treatment is to stop the first plasma after the oxidation treatment is completed, and then the plasma 2 is irradiated. . The substrate processing method of the item 13 of the scope, wherein the nitriding treatment and the nitriding treatment are performed by supplying oxygen to the plasma treatment, and the oxidation treatment is performed during the oxidation treatment. The substrate processing method of the first item, wherein the method is formed using microwaves. The substrate processing method of the range item 1, in which a microwave is emitted through a planar antenna member to shape _ Page 22