JP2000012518A - Method and apparatus for treating surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To remove reaction products and contaminant metals at once, to greatly reduce the processing time by continuously treating the surface of a work in two steps with specified substances to the downstream of a plasma. SOLUTION: In a first chamber 15, H, F, N atoms or compd. thereof are fed to the treating surface of an Si wafer 17 having a natural oxide deposit, here H2O, N2 or NH3 is fed, the evacuation is made after the treating ends, a gate valve 16 is opened to take the wafer 17 out to a carrying chamber, the wafer 17 is carried to a stage in a second chamber 45 where H and Cl atoms or compd. thereof are fed for treating the surface. Here H2 and Cl2 are mixed and fed. As a result, it is possible to remove reaction products and contaminating metals at the some time, to greatly reduce the processing time and improve the productivity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen-fluorine-based plasma downstream for treating a workpiece downstream of a plasma using at least hydrogen, fluorine, and nitrogen, for example, removing a silicon native oxide film on a silicon surface. Processing,
Hydrogen, chlorine to process the workpiece downstream of the plasma, for example, by performing continuous chlorine-based plasma downstream processing to remove contaminant metals on the semiconductor surface, to overcome the mutual processing issues, The present invention also relates to a plasma downstream surface treatment method capable of improving the treatment speed.

[0002]

2. Description of the Related Art Dry cleaning methods for treating a solid surface in a gas phase without using a solution to obtain a clean surface have been actively studied in recent years. However, even if it is a method of obtaining a clean surface at once, the actual processing contents are various. One of the most actively studied fields at present is the cleaning of semiconductor surfaces mainly composed of silicon. Taking this semiconductor surface cleaning as an example,
Originally, the cleaning technique was to remove contaminant organic matter, contaminant metal, and inorganic solid particles generally called particles from the semiconductor surface. However, for example, a very large scale integrated circuit (U
With the most advanced devices called LSIs, without managing and controlling the reactions at the atomic and molecular levels during the manufacturing process, it is possible to achieve not only the productivity of the devices but also the performance itself intended at the design stage. It has reached the stage where it cannot be done. Therefore, in recent cleaning treatments, in addition to the above three issues, optimization and securing of the degree of surface irregularities at the atomic level (surface morphology) and the chemical bonding state of surface constituent atoms (surface chemical structure) are newly added. Is recognized as an important issue. One of the subjects that has been actively studied recently as a part of improving the surface morphology and optimizing the surface chemical structure is removal of a native oxide film on a semiconductor surface.

One of the most well-known methods for removing a natural oxide film on a dry silicon surface is one that utilizes hydrofluoric anhydride (HF) vapor. This is a process of exposing a silicon substrate to a vapor of hydrofluoric anhydride diluted or not diluted with water vapor or the like to remove a natural oxide film on silicon. Hydrofluoric acid vapor forms a thin liquid layer of hydrofluoric acid and water condensed on the silicon surface,
It is believed that this removes the native oxide film. When only hydrofluoric anhydride is used, water condensing on the surface is generated by a chemical reaction between the silicon oxide film (SiO ₂ ) and hydrofluoric acid. Therefore, the reaction mechanism can be considered to be the same as the natural oxide film removal by the hydrofluoric acid solution diluted with water. (CR Helms and BE Dea
1, J .; Vac. Sci. Technol. A10,8
06 (1992). )

[0004] In the case of using plasma, a method of performing a process downstream of a mixed gas plasma of nitrogen trifluoride (NF ₃ ) and ammonia (NH ₃ ) (N. Nishino, NH).
ayasa, and H .; Okano, J. et al. App
l. Phys. , 74, 1345 (1993)), and a method of performing processing downstream of a mixed gas plasma of nitrogen trifluoride (NF ₃ ) and hydrogen (H ₂ ) (T. Kusuki, H. Ka).
Wakami, H .; Sakaue, and Y Hor
iike, Ext. Abstr. Electroche
medical Society, Hawaii (199
3) p. 375. ) Has been reported. Although the detailed reaction mechanism has not been elucidated in both cases, it is found that reactive products supposed to be (NH ₄ ) ₂ SiF ₆ are deposited on the surface after treatment in such a large amount that they can be visually confirmed, and both are heated in vacuum at about 100 ° C. Then, the product evaporates and fluorine remains on the surface, and other phenomena are common, and it is considered that the treatment is based on the same reaction.

[0005] Further, in a recently reported technique, nitrogen trifluoride (NF ₃ ) is mixed in the downstream of a plasma of a mixed gas of hydrogen (H ₂ ) and water vapor (H ₂ O), and silicon is installed further downstream. There is a method of removing a natural oxide film (JP-A-6-338478, and J. Kikuchi, M. et al.
Iga, S .; Fujimura, and H .; Yan
o, "Native oxide removal o
n Si surface by NF ₃ -added
hydrogen and water vapor
plasmadownstream treatmen
t ", Jpn. J. Appl. Phys., 33, 22.
07 (1994)). This is one using a phenomenon in which a hydrogen atom is a large amount transported downstream of the plasma of a mixed gas of H2 and H2 O, by adding NF3 downstream of the plasma, that the NF ₃ is dissociated in the plasma In addition, the generation of fluorine atoms which induces the generation of particles or deteriorates the device by etching the inner wall of the device with high reactivity is prevented. According to “Study on Dry Cleaning Technology for Silicon Surface in Integrated Circuit Manufacturing Process” (Jun Kikuchi, Ph.D. dissertation, 1997, Kyoto University), which examined this method in detail, it was found that the above-mentioned N.I. Nishino et al. Kusuki
In the same manner as in the case of the above, a reactive product presumed to be (NH ₄ ) ₂ SiF ₆ cannot be visually observed, but slightly covers the surface. Again, this reactive product can be rapidly evaporated by heating under reduced pressure. Nishino et al. Ku
The difference from suki and the like is that after the reaction product is removed, the surface of the hydrogen-terminated silicon is free of fluorine.
This difference is Nishino et al. It is thought that this is due to the fact that Kutsuki et al. Use fluorine atoms having a long life, while hydrogen atoms are used. For this reason, carbon was also removed from the surface after the treatment, indicating that this method is also effective for organic contamination. Of course, the amount of reaction products is small,
Since no fluorine atoms are generated, no particles are generated during the processing.

Further, Japanese Patent Application No. 1997-366109 discloses a method for realizing the same processing as that of JP-A-6-338478, although the mechanism is different. In this method, NF ₃ is added downstream of a plasma of a mixed gas in which a small amount of H ₂ or H ₂ O is mixed into a large amount of nitrogen (N ₂ ), and a silicon surface provided further downstream is treated. Since the removal rate of the amount and the natural oxide film necessarily in this way the hydrogen atoms is not proportional, JP-hydrogen atoms generated in the plasma are transported to the downstream NF ₃ and to chemical reaction 6-33
Unlike 8478, it is believed that the reaction is performed by the action of long-lived metastable nitrogen excited by the plasma.

In addition to the removal of the natural oxide film, several methods for removing contaminant metals in the gas phase have been studied. Chlorine (Cl ₂ ) while irradiating silicon or silicon oxide film with ultraviolet light
To remove contaminant metals (R. Sugin)
o, Y. Nara, T .; Yamazaki, S .; Wat
anabe, and T .; Ito, Ext. Abst
r. , 19th Conf. on SSDM, 207
(1987)) and a method of exposing the surface of a workpiece to hydrogen chloride (HCl) or hydrogen bromide (HBr) (USP Pa).
tent Number 5, 089, 441) and the like are known. However, the mechanism is unclear for both, and practicality and applicability are not so clear. For this reason, both technologies have been reported or applied for more than eight years, but have not been widely used in industry. In addition,
U. S. P. Patent Number 5,08
No. 9,441 also describes a method of simultaneously irradiating germane mixed with germane (GeH ₄ ) or hydrogen fluoride (HF) directly or removing a natural oxide film on a semiconductor substrate by plasma downstream processing using them. ing.

[0008]

It is known that the treatment with HF vapor produces a residue after removing a natural oxide film on a silicon substrate and also leaves fluorine. Although washing with water or the like is effective for removing the residue, the remaining fluorine reacts with water and immediately reoxidizes the surface. Since the reaction is basically the same as that of the hydrofluoric acid solution, a hole having a diameter of about 1 micron is formed in a thick PSG layer on a silicon substrate, for example, as in some electrode windows of recent ULSI, and a hole is formed at the bottom. For example, when a silicon natural oxide film on a certain silicon substrate is removed, the etching rate of HF vapor with respect to PSG is high, so that there is a disadvantage that the diameter of the hole is greatly increased. Further, the HF vapor treatment may roughen the silicon surface after the treatment, and has a disadvantage in securing the surface morphology. Further, besides the problem of the process itself with respect to such processing results, HF vapor processing can be used only under a certain pressure because HF condensation on the silicon substrate surface is an important factor in performing the processing. There is also a drawback in industrial use, such as poor compatibility with vacuum equipment in which many film forming processes are performed.

N. Nishino et al. Kusuki
The reason why such methods are not widespread is particles represented by a large amount of reaction products, and fluorine remaining after heating and evaporating the reaction products. In both cases, NF ₃ is used as a plasma source gas (a gas to be turned into plasma), so that the inner wall of the plasma generating container is easily etched by highly reactive fluorine ions or fluorine atoms. Quartz, alumina, aluminum, and the like are generally used for the inner wall of the plasma generation container, but all of them are etched or generate particles when exposed to fluorine-based gas plasma for a long time. In addition, this process uses long-lived fluorine atoms to perform surface treatment in the downstream region where the effects of charged particles in the plasma can be substantially ignored. It is impossible to eliminate the direct effect.

In this regard, the method for removing a silicon natural oxide film disclosed in Japanese Patent Application No. Hei. Nishino et al. Solving the problems of particles, residual fluorine, and surface roughness found in the method of Kutsuki et al. Among the items required for the surface cleaning described above, at least for the silicon surface cleaning, particle removal and contamination metal removal. Almost all of them have been solved for removing organic contaminants, securing surface morphology, and optimizing the surface chemical structure. Therefore, establishment of an effective dry cleaning technique can be expected if it can be combined with particle removal or contamination metal removal means. However, the 1997 patent application No. 36610
Also in the method of JP-A No. 9 and JP-A-6-338478, a very small amount of a reaction product remains on the surface after the treatment, and it is necessary to heat it to about 40 ° C. or more in a vacuum to remove the reaction product. That is, these methods are exactly two-stage processes of plasma downstream processing and heating processing. These processes mean that the temperature of the workpiece needs to be changed, since the plasma downstream processing itself has the advantage of cooling the workpiece in terms of processing speed. Therefore, when actually performing, after performing the plasma downstream processing on the cooling stage, the workpiece is lifted from the cooling stage and heated with light or the like, or a heating stage prepared separately from the plasma downstream processing Transporting the workpiece to
And other means are required, which imposes a heavy burden on the apparatus and processing speed.

[0011] A method for removing metals by ultraviolet rays and chlorine gas (U
V chlorine method) and U. S. P. One of the reasons why the method described in US Pat. No. 5,089,441 is not widely used seems to be processing instability. The actual contaminant metal is in the form of some compound such as oxide or silicide, and contaminant metal atoms rarely exist as they are. Although both of the above methods ultimately aim to remove the contaminating metal into chloride, the efficiency of chloride conversion naturally depends on the form in which the contaminating metal is present. In the UV chlorine method, a chemical bond is broken by the energy of ultraviolet light to separate a contaminant metal and react with chlorine. However, not all chemical bonds can be broken by ultraviolet light, and even if the metal is separated, it must react with chlorine before recombining and returning to the original compound. In addition, the energy enough to break the chemical bond of the metal compound should be sufficient to break the bond between the elements constituting the workpiece, and at this time, the workpiece will be damaged. U. S. P. 5,0
The effectiveness of the method of 89,441 is not clear because it does not show a specific contaminant metal removing effect, but the natural oxide film removal by germane is performed at 650 to 800 ° C., and the temperature is considerably high. At such a high temperature, the contaminant metal easily diffuses into the silicon or silicon oxide film, and may instead introduce the contaminant metal into the semiconductor substrate.

[0012]

A first step of supplying atoms of hydrogen, fluorine, nitrogen, or compounds thereof downstream of the first plasma to treat the surface of the workpiece;
Downstream of the second plasma, a second step of treating the surface of the workpiece by supplying hydrogen or chlorine atoms or compounds thereof is continuously performed.

The method disclosed in Japanese Patent Application No. 366109/1997 and Japanese Patent Application Laid-Open No. 6-338478 substantially satisfy the requirements for surface cleaning except for the removal of contaminant metals and particles as described above. The problem was inefficiency due to the two-step process, but if the subsequent heat treatment also serves as particle removal and contaminant metal removal,
This is a more complete dry cleaning technology. However, no effective method or principle for removing particles in the gas phase has been found. On the other hand, in wet processing, particles adhere,
Theories that discuss elimination have been developed and are steadily producing results. Therefore, for the time being, removal of contaminated metals has become a more promising subject from the viewpoint of dealing with microfabrication for dry cleaning.

The UV chlorine method and U.S.A. S. P. 5,089,4
In the method shown in FIG. 41, the silicon substrate is heated for the processing itself, and at first glance it is also used as the second-stage heating processing in the processing of 1997 Patent Application No. 366109 and JP-A-6-338478. It seems like. However, the simple connection of those technologies is based on the processing results of 1997 Patent Application No. 366109 and Japanese Patent Application Laid-Open No. 6-338478 in terms of securing surface morphology such as damage and surface roughness, and optimizing the surface chemical structure. Rather, it will deteriorate. Therefore, for the removal of contaminating metals, the UV chlorine method or U.S. S. P. It is necessary to use means different from the method shown in 5,089,441.

[0015] In the silicon natural oxide film removal process disclosed in Japanese Patent Application No. 366109/1997 and JP-A-6-338478, it is known that the silicon surface after evaporating the reaction product is terminated with hydrogen. Have been. It is known that a silicon surface terminated with hydrogen is more stable than a surface not terminated with hydrogen, and is not immediately oxidized or etched by fluorine even when irradiated with oxygen molecules or XeF ₂ (H Ogawa, K. Ishik
awa, M .; Aoki, S .; Fujimura, N .; U
eno, Y .; Horiike, and Y. Harad
a, "Observation of oxygen"
exposed hydrogen terminat
ed silicon surface ”, The P
physics and Chemistry of S
iO2 and the Si-SiO2 Inter
face 3, edited by H. Z. Mass
aud, E .; H. Pointdexter, and C.I.
R. Helms, The Electrochemical
l Society, NJ, p. 428 (1996).
And Y. Morikawa, K .; Kubota, H .; O
gawa, T .; Ichiki, A .; Tachiban
a, S. Fujimura, and Y .; Horik
e, "Reaction of the fluori
ne atom and molecular with
the hydrogen-terminated
Si (111) surface ", J. Vac. Sc
i. Technol. A16, 345 (199
8). ). Naturally, similar effects can be expected for chlorine. Although this is not in the gas phase, the dissolved oxygen concentration is 1p
that even if a hydrogen-terminated silicon surface is acted on hydrofluoric acid diluted in water of pb or less, it is hardly etched;
Similarly, it has been reported that the effect of hydrochloric acid (HCl) diluted with water having a dissolved oxygen concentration of 1 ppb or less does not change the surface morphology or the hydrogen-terminated structure. That is, when a chlorine-based gas is caused to act on the hydrogen-terminated silicon surface, there is a possibility that the contaminant metal can be removed without changing the surface morphology or surface chemical structure. However, irradiation with UV light or a high temperature of 450 ° C. or more desorbs hydrogen from silicon. That is, UV chlorine method and U.
S. P. In the method disclosed in 5,089,441, hydrogen is removed from silicon, and a reaction between chlorine and a contaminant metal is promoted in a state where silicon and chlorine are easily reacted. Therefore, silicon is inevitably etched. Also, the hydrogen-terminated surface is lost.

According to the invention previously filed by the same inventor as the present invention, accession number 29809000040, even when a chlorine-based gas is mixed with hydrogen, a large amount of hydrogen atoms are carried downstream of the plasma of the mixed gas. It has been shown. In particular, when chlorine gas (Cl ₂ ) or hydrogen chloride molecule (HCl), which does not contain oxygen as a chlorine-based gas, is used, it is possible to completely eliminate the influence of oxygen. It is shown that At the same time, it is shown that the natural oxide film on the metal surface can be reduced and removed, which indicates that this method is also effective for removing oxidized contaminant metals. Hydrogen atoms are known to recombine inside the metal or on the metal surface to return to hydrogen molecules, at which time they release energy as heat. Therefore, the metal fine particles and the like are selectively heated to promote the reaction between chlorine and the metal. It has also been reported that hydrogen atoms have the effect of removing fluorine and chlorine from fluorinated silicon. However, when the method of accession number 29809000040 is used as a contaminant metal removing means, N.I. Nishin
o et al. It was possible to remove fluorine from the surface where fluorine remained after the treatment by the method of Kutsuki et al. This is because Nishino et al. Kutsuki et al., And 1997 Patent Application No. 3661.
09, JP-A-6-338478 and reception number 298
09000040 This is an effect that is not easily expected from each finding alone.

Accordingly, the present invention is not limited to the method disclosed in 1997 Patent Application No. 366109 or JP-A-6-338478.
N. Nishino et al. Even in a silicon natural oxide film removal treatment in which fluorine may remain on the surface after the treatment as in the method of Kutsuki et al., The workpiece is subsequently kept at a temperature of room temperature or higher, for example, at least hydrogen, By performing the treatment downstream of the plasma using a gas containing chlorine as a constituent element, it is possible to simultaneously remove the reaction products generated during the natural oxide film removal reaction and to remove the contaminant metals. Can be shortened.

In the present invention, since the first step and the second step can be continuously performed in a vacuum using a single or a plurality of processing apparatuses, for example, a gas containing oxygen as a main component is used. It is also possible to perform a series of surface treatments by connecting the processing equipment to various types of organic substances removal processing using plasma or plasma downstream, various CVD, sputtering film formation processing, etc. It is.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 One chamber type H
The wafer is lifted after removing the natural oxide film in the -NF system.
A device that performs H-Cl treatment while heating R.

FIG. 2 Two-chamber type load lock (transfer chamber) is connected.

[0021]

EXAMPLE [First Example] A dry cleaning process was performed using the apparatus shown in FIG. A 6-inch silicon wafer with a natural oxide film was used as a workpiece, and the H ₂ O flow rate was 10 sc.
cm, in the first chamber, _{N 2} flow rate 190scc
m, microwave power 500 W, added NF ₃ flow rate 100
The processing was performed under the conditions of sccm, processing pressure of 2 Torr, and processing time of 3 minutes. At this time, the stage temperature of the first chamber was adjusted and cooled so that the wafer temperature was maintained at 10 ° C. After the processing, the gas is exhausted, the gate valve is opened, and the wafer is taken out to the transfer chamber. After closing the gate valve of the first chamber, the gate valve of the second chamber is opened, and the wafer is transferred to the stage of the second chamber. The stage temperature of the second chamber is set between 120 and 250 ° C., but was set to 180 ° C. in this embodiment. The reason why the gate valve of the first chamber and the gate valve of the second chamber were not opened at the same time is that the stage is heated to the second chamber,
This is to prevent the water vapor used in the processing in the first chamber from entering and oxidizing the silicon wafer.

In the second chamber, the gate valve is closed and 90 sccm of hydrogen molecules flow, and then the lift pins are lowered and the wafer is placed on the stage. Next, chlorine molecule 10sccm
And a microwave of 500 W, 2.45 GHz is applied to form a plasma, and the processing time is 3 at a processing pressure of 2 Torr.
Minutes of processing.

After the treatment in the second chamber, the wafer surface removed from the apparatus through the load lock was water repellent. Even after being left in the air for 30 minutes, the wafer surface maintained water repellency, which suggests that the silicon wafer surface had a hydrogen-terminated structure and that there was substantially no residual fluorine that promotes oxidation. Therefore, in order to obtain a hydrogen-terminated surface after the treatment performed in the first chamber of this embodiment for removing the silicon natural oxide film, for example, 100 ° C., 6 ° C.
Heat treatment for 0 to 120 seconds was required, but this treatment could be omitted here. For example, when 50 silicon wafers are processed, the processing time is shortened by 2 to 3 hours as compared with the case where the natural oxide film removal and the contamination metal removal are performed by separate apparatuses.

Second Embodiment Washing with sulfuric acid / hydrogen peroxide solution, washing with hydrochloric / hydrogen peroxide solution, and washing with diluted hydrofluoric acid were performed.
A natural oxide film (chemical oxide film) contaminated with Fe by immersing an inch-sized silicon wafer in a mixed solution of ammonia and hydrogen peroxide which is forcibly contaminated by adding a standard solution for atomic absorption analysis of iron (Fe). Was formed. A 5% hydrofluoric acid solution was dropped on the wafer surface to etch an oxide film on the surface. When the dropped 5% hydrofluoric acid was recovered, the Fe concentration was measured by the atomic absorption method, and the surface density of Fe was calculated.
¹³ atom / cm ² .

Next, the same contaminated wafer is subjected to the same dry cleaning treatment as in the first embodiment, and 5% hydrofluoric acid is dropped on the surface of the taken-out wafer to spread the liquid over the surface. After collecting, measure the Fe concentration by atomic absorption
When the surface density of e was calculated, this time, about 5 × 10 ¹¹
atom / cm ² , indicating that the contaminated metal was removed by the dry cleaning treatment according to the present invention.

[Third Embodiment] In the first chamber plasma generator of the apparatus of FIG. Simulating the method of Kutsuki et al., Flow NF ₃ 40 sccm and H ₂ 60 sccm,
Microwave power 500W, NF3 flow rate 100sc
cm, a processing pressure of 2 Torr, a wafer temperature of 10 ° C., and a processing time of 3 minutes. The quartz chamber from the plasma generation part of the first chamber to the processing part became cloudy, and it was visually confirmed from outside the apparatus that the reaction product was deposited on the wafer. After the treatment in the first chamber, the wafer was taken out of the apparatus after performing the hydrogen-chlorine plasma downflow treatment in the second chamber by the same operation as in the [first embodiment]. The wafer surface is water-repellent immediately after being taken out of the apparatus and after being left in the atmosphere for 30 minutes.
This was consistent with the processing result of [First Embodiment]. Therefore, by performing the process indicated by the reception number 29809000040 as the second step, N.N. Nishino et al. It was shown that the method of Kusuki et al. Could be used.

[0027]

As described above, the first step of supplying the atoms of hydrogen, fluorine, nitrogen, or their compounds downstream of the first plasma to treat the surface of the workpiece, By continuously performing the second step of treating the surface of the workpiece by supplying atoms or compounds of hydrogen and chlorine downstream of the plasma, for example, in the treatment of a silicon surface, a silicon natural oxide film The removal of the reaction product and the removal of the contaminated metal in the removal treatment can be performed at the same time, so that the treatment time can be greatly reduced and the productivity has been improved. In addition, by combining the first step and the second step, the natural oxide film removal process, which was previously considered unsuitable for mass production, can be used as the first step process, compensating for its disadvantages Becomes
The applicability of processing could be extended.

[Brief description of the drawings]

FIG. 1 shows a one-chamber type H-N-F-based system after removing a natural oxide film, lifting a wafer, and heating the wafer by IR heating.
It is a figure explaining the apparatus which performs Cl processing.

FIG. 2 is a diagram illustrating a two-chamber type apparatus. The chambers are connected via a load lock (transfer chamber).

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... First chamber microwave power supply 2 ... First chamber magnetron oscillator 3 ... First chamber microwave launcher 4 ... First chamber waveguide 5 ... First chamber Quartz plasma discharge part 6 ... First chamber Gas A supply flow control 7: First chamber gas B supply flow rate controller 8: First chamber gas C supply flow rate controller 9: First chamber Plasma discharge chamber lower block 10: First chamber Plasma discharge section support 11: First chamber gas C supply Unit 12: first chamber lamp heating reflector 13 ... first chamber lamp heating light source lamp 14 ... first chamber chamber inner wall quartz 15 ... first chamber chamber 16 ... first chamber gate valve 17 ... first chamber subject 18 ... First chamber Cooled object stage 19… One chamber cooling water passage 20 ... first chamber pin vertical drive unit 21 ... first chamber vacuum piping 22 ... first chamber pressure control butterfly valve 23 ... first chamber vacuum opening and closing valve 24 ... first chamber vacuum pump 31 ... second chamber micro Wave power supply 32 ... second chamber magnetron oscillator 33 ... second chamber microwave launcher 34 ... second chamber waveguide 35 ... second chamber quartz plasma discharge unit 36 ... second chamber gas D supply flow controller 37 ... second chamber Gas E supply flow controller 38 ... second chamber Gas F supply flow controller 39 ... second chamber Plasma discharge chamber lower block 40 ... second chamber plasma discharge part support 41 ... second chamber gas C supply part 42 ... second chamber Lamp heating Reflecting plate 43 ... second chamber lamp heating light source lamp 44 ... second chamber chamber inner wall quartz 45 ... second chamber chamber 46 ... second chamber gate valve 47 ... second chamber Workpiece 48 ... second chamber lower chamber plate 49 ... Second chamber resistance heating wire for processing table 50 Second chamber pin vertical drive unit 51 Second chamber vacuum pipe 52 Second chamber pressure control butterfly valve 53 Second chamber vacuum open / close valve 54 Second chamber vacuum pump 55 … Load lock vacuum pre-chamber / object transfer unit 56… Load lock chamber Object transfer robot

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroki Ogawa 2-18-18 Shin-Yokohama, Kohoku-ku, Yokohama-shi, Kanagawa 1st Century Shin-Yokohama 701 F-term (reference) 5F004 AA14 BA19 BA20 BB14 CA04 DA04 DA17 DA24 DA25 DA29 DB03 EA28

Claims (11)

[Claims] 1. A first step of supplying atoms of hydrogen, fluorine, nitrogen, or a compound thereof to treat a surface of a workpiece downstream of a first plasma, and a step of supplying hydrogen downstream of a second plasma. And a second step of continuously treating the surface of the workpiece by supplying atoms or compounds of chlorine or a compound thereof. 2. The method according to claim 1, wherein the first step comprises hydrogen, fluorine, nitrogen,
Helium, neon, argon, krypton, xenon,
And, downstream of the first plasma which is a plasma of a gas containing at least one element of radon, hydrogen, fluorine, a gas containing all the elements not contained in the first plasma among nitrogen, and further downstream thereof 2. The surface treatment method according to claim 1, wherein the processing is performed by placing a workpiece on the workpiece. 3. The first step is performed by mixing a gas containing nitrogen trifluoride (NF3) downstream of the first plasma in which a gas containing molecules containing hydrogen as a constituent element is turned into plasma. 3. The surface treatment method according to claim 2, wherein: 4. The method according to claim 1, further comprising the step of: downstream of a plasma of a gas containing at least one element of hydrogen, chlorine, nitrogen, helium, neon, argon, krypton, xenon, and radon. 2. The surface treatment method according to claim 1, wherein a gas containing all elements not contained is mixed therein, and the workpiece is further disposed downstream to perform the treatment. 5. The second step is performed by mixing a gas containing a molecule containing chlorine atoms as a component downstream of the second plasma in which a gas containing molecules containing hydrogen as a component is turned into plasma. The surface treatment method according to claim 4, wherein: 6. The surface treatment method according to claim 1, wherein the second plasma in the second step is obtained by converting a gas containing at least hydrogen and chlorine into a plasma. 7. The method according to claim 1, wherein the first step and the second step are performed continuously by changing the supplied gas in one reduced pressure vessel. Surface treatment method. 8. The surface treatment method according to claim 1, wherein each of the first step and the second step is performed in a separate vacuum vessel. 9. The surface treatment method according to claim 1, wherein the first step is performed by cooling the workpiece. 10. The surface treatment method according to claim 1, wherein the second step is performed while maintaining the workpiece at a temperature equal to or higher than room temperature. 11. A plasma downstream processing module comprising at least two plasma processing units each comprising a plasma generating unit and a processing unit which communicates with the plasma generating unit and processes the workpiece.
The two plasma downstream processing modules are separated by a gate valve and depressurized or nitrogen,
Connected through a transfer chamber filled with an inert gas, at least one of the plasma downstream processing modules is provided with a gas inlet through which a gas containing a molecule containing a fluorine atom as a component is introduced, and at least the other. A surface treatment apparatus characterized in that the plasma downstream treatment module is provided with a gas inlet for introducing a gas containing molecules containing chlorine atoms as constituent elements.