CN107026080B - Substrate processing method, substrate processing apparatus, and substrate processing system - Google Patents

Substrate processing method, substrate processing apparatus, and substrate processing system Download PDF

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CN107026080B
CN107026080B CN201710007284.0A CN201710007284A CN107026080B CN 107026080 B CN107026080 B CN 107026080B CN 201710007284 A CN201710007284 A CN 201710007284A CN 107026080 B CN107026080 B CN 107026080B
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wafer
atmosphere
substrate
temperature
substrate processing
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CN107026080A (en
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羽田敬子
清水昭贵
长仓幸一
立花光博
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Tokyo Electron Ltd
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    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
    • H01L21/02312—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a gas or vapour
    • H01L21/02315—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a gas or vapour treatment by exposure to a plasma
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    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3065—Plasma etching; Reactive-ion etching
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    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
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    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
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    • H01L21/67017—Apparatus for fluid treatment
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    • H01L21/6704—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for wet cleaning or washing
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    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67098—Apparatus for thermal treatment
    • H—ELECTRICITY
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    • H01L2924/01—Chemical elements
    • H01L2924/01009—Fluorine [F]

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Abstract

The invention provides a substrate processing method, a substrate processing apparatus and a substrate processing system, which can remove residual fluorine with a simple structure and without reducing the productivity. The wafer (W) subjected to COR processing and PHT processing in the process module (13) is exposed to humidity in a processing chamber (28) of a refrigeration unit (20) and is adjusted so that the moisture content contained therein is 50g/m3The above atmosphere.

Description

Substrate processing method, substrate processing apparatus, and substrate processing system
Technical Field
The present invention relates to a substrate processing method, a substrate processing apparatus, and a substrate processing system for removing fluorine remaining on a surface of a substrate.
Background
As a process for removing an Oxide film formed on a semiconductor wafer (hereinafter, simply referred to as "wafer") as a substrate by Chemical etching, for example, COR (Chemical Oxide Removal) process and PHT (Post Heat Treatment) process are known. In the COR process, an oxide film formed on the surface of a wafer is reacted with hydrogen fluoride gas and ammonia gas, and Ammonium Fluorosilicate (AFS) as a reaction product is generated from the oxide film. In the PHT process, the wafer is heated to sublimate and remove the generated AFS. That is, the oxide film is removed by the COR process and the PHT process.
However, fluorine may remain on the surface of the wafer after the COR process and the PHT process are performed. The remaining fluorine may corrode a wiring film or the like formed on the surface of the wafer, thereby deteriorating the electrical characteristics of a semiconductor device manufactured from the wafer. Therefore, it is necessary to remove fluorine remaining on the surface of the wafer (hereinafter referred to as "residual fluorine").
As a method for removing residual fluorine, conventionally, wafer processing has been carried outA wet cleaning method using DHF (dilute hydrofluoric acid) and DIW (pure water) as cleaning liquids was applied. When the wafer is subjected to wet cleaning, the number of fluorine atoms remaining on the surface of the wafer can be reduced to 10 per 1 cm12The level of (c).
However, with the miniaturization of the wiring and the like of the semiconductor device, the width of the pattern formed on the surface of the wafer becomes several nm, and therefore, there is a problem that the pattern collapses due to the surface tension of the cleaning liquid. Therefore, a method of removing residual fluorine by using plasma without using a cleaning liquid has been proposed. In this method, oxygen plasma is generated in the vicinity of the surface of the wafer, and fluorine is forcibly replaced and removed (see, for example, patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese Kohyo publication (Kohyo publication) No. 2012-532440
Disclosure of Invention
Problems to be solved by the invention
However, in the method of patent document 1, a mechanism for generating oxygen plasma is required. Further, since a step such as pressure reduction is required to generate oxygen plasma, and this step requires a constant time, there is a problem that productivity is lowered.
The invention aims to provide a substrate processing method, a substrate processing device and a substrate processing system which have simple structures and can remove residual fluorine without reducing the productivity.
Means for solving the problems
In order to achieve the above object, a substrate processing method according to the present invention includes a 1 st step of performing a process using a fluorine-containing gas on a substrate and a 2 nd step of exposing the substrate to an atmosphere containing moisture.
In order to achieve the above object, a substrate processing apparatus according to the present invention includes: a processing chamber for accommodating a substrate subjected to a process using a fluorine-containing gas; and a moisture containing mechanism for containing moisture in the atmosphere in the processing chamber.
In order to achieve the above object, a substrate processing system includes: a substrate processing apparatus that performs a process using a gas containing fluorine on a substrate; and a post-treatment apparatus that exposes the substrate subjected to the treatment using the fluorine-containing gas to an atmosphere containing moisture.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a substrate subjected to a treatment using a fluorine-containing gas is exposed to an atmosphere containing moisture. Fluorine is combined with hydrogen in the moisture to become hydrogen fluoride, and sublimed and removed. Fluorine on the surface of the substrate, which terminates silicon (end in Japanese), is replaced with hydrogen and hydroxyl groups in the water and removed. That is, since fluorine can be removed from the substrate only by exposure to an atmosphere containing moisture, a mechanism or a process for generating plasma is not necessary. As a result, the residual fluorine can be removed with a simple structure without lowering the productivity.
Drawings
Fig. 1 is a plan view schematically showing the configuration of a substrate processing system according to an embodiment of the present invention.
Fig. 2 is a sectional view schematically showing the structure of the refrigerating unit in fig. 1.
FIG. 3 is a graph showing the number of residual fluorine atoms when a wafer having residual fluorine on the surface thereof is stored in a constant temperature and humidity chamber.
Fig. 4 is a process diagram for explaining a process of reducing the number of residual fluorine atoms in the embodiment of the present invention.
Fig. 5 is a graph showing the number of residual fluorine atoms when the moisture content of the atmosphere to which the wafer is exposed is changed.
Fig. 6 is a graph showing the number of residual fluorine atoms when the time for exposing the wafer to the high-humidity atmosphere is changed.
Fig. 7 is a flowchart showing an oxide film removal process as a substrate processing method according to an embodiment of the present invention.
Description of the reference numerals
W, a wafer; 10. a substrate processing system; 13. a process module; 20. a cold storage section; 29. a moisture supply mechanism.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
Fig. 1 is a plan view schematically showing the configuration of a substrate processing system according to an embodiment of the present invention. In fig. 1, a part of the internal structure is shown in a perspective view for easy understanding.
In fig. 1, a substrate processing system 10 includes: a wafer storage 11 for storing a plurality of wafers W; a transfer module 12 as a common transport unit that transports two wafers W simultaneously; the plurality of process modules 13 (substrate processing apparatuses) perform COR processing and PHT processing on the wafers W input from the transfer module 12. The interior of the process module 13 is maintained as a vacuum atmosphere.
In the substrate processing system 10, two wafers W selected from the plurality of wafers W stored in the wafer storage 11 are held by a transfer arm 14 built in the transfer module 12, the wafers W are transferred inside the transfer module 12 by moving the transfer arm 14, and 1 wafer W is placed on each of two stages 15 arranged inside the process module 13. Next, in the substrate processing system 10, after the COR process and the PHT process are performed on each wafer W placed on the stage 15 by the process module 13, the two processed wafers W are held by the transfer arm 14, and are transferred to the wafer storage 11 by moving the transfer arm 14.
The wafer storage 11 includes: 3 loading units 17 serving as tables of the front opening unified pod 16 serving as a container for storing a plurality of wafers W; a loading module 18 for receiving the stored wafers W from the foup 16 placed on each loading unit 17 or handing over the wafers W subjected to a predetermined process by the process module 13 to the foup 16; two load-lock modules 19 that temporarily hold the wafer W in order to transfer the wafer W between the load module 18 and the transfer module 12, and a cold storage unit 20 (substrate processing apparatus, post-processing apparatus) that cools the wafer W subjected to the PHT process.
The loading module 18 is constituted by a rectangular case having an atmospheric pressure atmosphere inside, and a plurality of loading portions 17 are provided in parallel on one side of the long sides constituting the rectangle. The loading module 18 includes a transfer arm (not shown) movable in the longitudinal direction of the rectangle inside. The transfer arm transfers the wafer W from the foup 16 placed on each loading unit 17 to the load lock module 19, or transfers the wafer W from the load lock module 19 to each foup 16. The front opening foup 16 accommodates a plurality of wafers W in a manner of stacking the plurality of wafers W in multiple stages. The interior of the foup 16 placed on each loading unit 17 is filled with nitrogen gas or the like and sealed.
Each load lock module 19 temporarily holds the wafer W in order to transfer the wafer W accommodated in the front opening foup 16 placed in each loading portion 17 of the atmospheric atmosphere to the process module 13 having a vacuum atmosphere therein. Each load lock module 19 has a stocker 21 that holds two wafers W. Each load-lock module 19 has a gate valve 22a for ensuring airtightness with respect to the loading module 18 and a gate valve 22b for ensuring airtightness with respect to the transfer module 12. A gas introduction system and a gas exhaust system, not shown, are connected to the load lock module 19 by pipes, and the inside is controlled to be an atmospheric pressure atmosphere or a vacuum atmosphere by the gas introduction system and the gas exhaust system.
The transfer module 12 inputs unprocessed wafers W from the wafer storage 11 to the process module 13, and outputs processed wafers W from the process module 13 to the wafer storage 11. The transfer module 12 is configured by a rectangular housing having a vacuum atmosphere inside, and includes two transfer arms 14 that can move while holding two wafers W, a rotary table 23 that rotatably supports each transfer arm 14, a rotary stage 24 on which the rotary table 23 is mounted, and a guide rail 25 that guides the rotary stage 24 so that the rotary stage 24 can move in the longitudinal direction of the transfer module 12. In addition, the transfer module 12 communicates with the load-lock module 19 of the wafer storage 11 and each process module 13 via the gate valves 22a, 22b, and also via each gate valve 26 discussed later. In the transfer module 12, the transfer arm 14 holds and receives two wafers W held by the stocker 21 in the load lock module 19, and transfers the wafers W to each process module 13. The transfer arm 14 holds two wafers W processed by the process module 13 and outputs the wafers W to the load lock module 19. The rotation table 24 and the guide rail 25 constitute a slide mechanism for moving the placed rotation table 23 in the longitudinal direction inside the transfer module 12.
Each process module 13 communicates with the transfer module 12 via a respective gate valve 26. Therefore, the gate valves 26 ensure airtightness between the process modules 13 and the transfer module 12 and communicate with each other. The process module 13 is connected to a gas introduction system (a gas supply unit for a process gas, a purge gas, and the like) and a gas exhaust system (a vacuum pump, an exhaust control valve, an exhaust pipe, and the like), which are not shown.
Each process module 13 includes two stages 15 on which two wafers W are placed in a horizontal direction. The process modules 13 process the surfaces of the two wafers W uniformly and simultaneously by placing the wafers W on the two stages 15 in a row. In the present embodiment, the plurality of process modules 13 each perform either one of the COR process and the PHT process.
The substrate processing system 10 further includes a controller 27 as a control unit, and the controller 27 controls operations of the respective components of the substrate processing system 10 by executing a program or the like stored in a built-in memory or the like.
Fig. 2 is a sectional view schematically showing the structure of the refrigerating unit in fig. 1.
In fig. 2, the refrigerating unit 20 includes a processing chamber 28 for accommodating the wafer W, a moisture supply mechanism 29 (moisture containing mechanism), an inert gas supply mechanism 30, and an exhaust mechanism 31.
The processing chamber 28 is maintained at atmospheric pressure, and a stage 32 on which the wafer W is placed is disposed. The stage 32 incorporates a heater 33 for heating the wafer W placed thereon and a cooling passage 34 for cooling the wafer W. The stage 32 adjusts the temperature of the wafer W placed thereon by the heater 33 and the cooling passage 34. The processing chamber 28 has a port 35 as a through-hole in a side wall portion thereof, and the wafer W is input to and output from the processing chamber 28 through the port 35. The port 35 is closed by a gate valve 36 which can be opened and closed.
The water supply mechanism 29 is composed of a water supply unit 37 and a pipe 38, and the atmosphere in the processing chamber 28 contains water as water vapor. The inert gas supply mechanism 30 is composed of a gas supply unit 39 and a pipe 40, and supplies an inert gas, for example, nitrogen gas into the processing chamber 28. The exhaust mechanism 31 is composed of an exhaust pump 41 and a pipe 42, and exhausts the inside of the processing chamber 28.
In the present embodiment, the PHT treatment is performed on the wafer W, but the PHT treatment is a treatment of sublimating AFS generated on the wafer W by heating, and therefore, the temperature of the wafer W subjected to the PHT treatment is high, for example, about 120 ℃. The refrigerator 20 cools the wafer W subjected to the PHT process.
However, before the present invention, the present inventors prepared a plurality of samples of the wafer W having residual fluorine on the surface thereof in order to find an appropriate method for removing residual fluorine other than the removal by wet cleaning or oxygen plasma, and performed various experiments, and as a result, they temporarily stored these samples in a clean room in advance, and found that the number of residual fluorine atoms on the surface of each sample was significantly reduced. The inside of the clean room was an atmospheric pressure atmosphere, and the appropriate humidity was maintained, and therefore, the inventors of the present invention assumed that moisture contributes to reduction in the number of residual fluorine atoms. Then, the present inventors prepared a plurality of samples of the wafer W having fluorine residues on the surface thereof, accommodated the samples in a constant temperature and humidity chamber in which the temperature and humidity were controlled, changed the conditions of the temperature and humidity in the constant temperature and humidity chamber, and measured the number of fluorine residues under each condition.
FIG. 3 is a graph showing the number of residual fluorine atoms when a wafer having residual fluorine on the surface thereof is stored in a constant temperature and humidity chamber.
As the wafer W having residual fluorine on the surface, wafers W after COR processing and PHT processing were used. The number of residual fluorine atoms on the wafer W is 5.0X 10 per 1 cm14. In fig. 3, "×" indicates the number of residual fluorine atoms under each condition when the conditions of temperature and humidity inside the thermostatic and humidistatic tank were changed. In addition, in the chart of FIG. 3The number of residual fluorine atoms when the wafer W after COR processing and PHT processing, which are objects of comparison, was placed in the cleaning chamber is represented by "◆". The abscissa of the graph of FIG. 3 represents the elapsed time from the wafer W being placed in the constant-temperature and constant-humidity chamber and the time of placement in the cleaning chamber.A condition in which the temperature and humidity inside the constant-temperature and constant-humidity chamber were changed is represented by a condition in which the temperature was 24 ℃ and the humidity was 95%, a condition in which the temperature was 48 ℃ and the humidity was 75%, a condition in which the temperature was 48 ℃ and the humidity was 80%, a condition in which the temperature was 60 ℃ and the humidity was 55%, a condition in which the temperature was 60 ℃ and the humidity was 70%, and a condition in which the temperature was 60 ℃ and the humidity was 95%.
As shown in the graph of FIG. 3, when the wafer W is placed in the cleaning chamber, the number of fluorine atoms remaining when the wafer W is not subjected to any treatment is reduced to 10 per 1 square centimeter, which is the number of fluorine atoms present on the surface of the wafer W12A considerable time (about 72 hours) is required for the level of (b) (hereinafter referred to as "standard residual fluorine atom number level"). On the other hand, when the wafer W is exposed to a high-humidity atmosphere in the constant-temperature and constant-humidity chamber, the number of residual fluorine atoms is reduced to the reference residual fluorine atom number level in about 10 minutes.
However, since the moisture saturation amount of the atmosphere changes depending on the temperature, the present inventors have conceived that the moisture amount in the atmosphere decreases by about the number of residual fluorine atoms, and have summarized the moisture amount and the number of residual fluorine atoms under the above-described conditions when the wafer W is exposed to the atmosphere of high humidity in the constant-temperature constant-humidity chamber in table 1 below.
[ TABLE 1 ]
Figure BDA0001203508170000081
As can be seen from the unshaded parts of the above table: the amount of water in the atmosphere is 20g/m3Above, the number of residual fluorine atoms present is reduced to 10 per 1 square centimeter13The amount of water in the atmosphere may be 50g/m3As described above, the number of residual fluorine atoms is reduced to approximately the standard residual fluorine atom number level.
The reason why the number of residual fluorine atoms is greatly reduced when the amount of moisture in the atmosphere is increased is difficult to clearly explain, but the present inventors have analogized the assumption of the following explanation as a result of the observation of the process of reducing the number of residual fluorine atoms.
First, fluorine alone is present on the surface of the wafer W subjected to the COR process and the PHT process, and silicon exposed on the surface of the wafer W by the removal of the oxide film is terminated with fluorine (fig. 4 (a)).
Next, when the surface of the wafer W is exposed to an atmosphere containing moisture, that is, a high humidity atmosphere, a part of the moisture in the atmosphere is decomposed into hydrogen and hydroxyl groups ((B) of fig. 4). At this time, hydrogen combines with fluorine of the monomer to become hydrogen fluoride, and sublimes. Fluorine that blocks silicon on the surface of the wafer W is replaced with hydrogen or hydroxyl and removed (fig. 4 (C)). As a result, the number of residual fluorine atoms on the surface of the wafer W is greatly reduced. Then, the silicon is stabilized by hydrogen and hydroxyl groups on the surface of the wafer W ((D) of fig. 4).
However, in the measurement of the amount of residual fluorine atoms, the temperature inside the constant temperature and humidity chamber is substantially the same as the temperature of the wafer W, and thereafter, the amount of residual fluorine atoms is measured under the condition that the temperature of the wafer W is lower than the temperature inside the constant temperature and humidity chamber, and as a result, moisture in the atmosphere condenses on the surface of the wafer W, and condensation occurs. If dew condensation occurs, the pattern may collapse due to the surface tension of the condensed moisture. On the other hand, in order to prevent the occurrence of dew condensation, the temperature of the wafer W needs to be higher than the temperature inside the constant temperature and humidity chamber. Therefore, from the viewpoint of reliably preventing the pattern from collapsing on the wafer W, it is preferable that the wafer W is heated so that the temperature of the wafer W becomes higher than the temperature inside the constant temperature and humidity chamber, that is, the temperature of the atmosphere.
On the other hand, if the temperature of the wafer W is set higher than the temperature of the atmosphere, moisture is less likely to adhere to the surface of the wafer W, and bonding of hydrogen and fluorine on the surface of the wafer W as described in fig. 4 and replacement of fluorine with hydroxyl groups that block silicon do not proceed so much, and as a result, the number of residual fluorine atoms is not reduced so much. For example, when the wafers W after the COR process and the PHT process are exposed to the atmosphere having the same moisture amount, the number of residual fluorine atoms changes depending on whether the wafers W are heated, and specifically, as shown in table 2 below, the number of residual fluorine atoms in the case where the wafers W are heated is increased as compared with the number of residual fluorine atoms in the case where the wafers W are not heated.
[ TABLE 2 ]
Figure BDA0001203508170000101
Therefore, in order to find the upper limit of the temperature of the wafer W, the present inventors exposed the wafer W to a predetermined moisture content (for example, 88.5 g/m) after the temperature of the wafer W after the COR process and the PHT process is changed3) The following table 3 shows the results of measuring the number of residual fluorine atoms in the atmosphere of (1): the number of residual fluorine atoms is not reduced to the reference residual fluorine atom number level as long as the difference between the temperature of the wafer W and the temperature of the atmosphere (the temperature inside the constant-temperature constant-humidity chamber) is substantially 100 ℃, and the number of residual fluorine atoms is reduced to the reference residual fluorine atom number level as long as the difference between the temperature of the wafer W and the temperature of the atmosphere is substantially 50 ℃.
[ TABLE 3 ]
Figure BDA0001203508170000102
In addition, it is considered that: even when the wafer W is heated, the combination of hydrogen and fluorine on the surface of the wafer W and the replacement of the silicon-terminated fluorine by the hydroxyl group are promoted as long as the moisture amount in the atmosphere is increased, and therefore, the present inventors have summarized the measurement of the number of residual fluorine atoms when the moisture amount of the atmosphere to which the wafer W is exposed after the COR treatment and the PHT treatment is changed in the graph of fig. 5. At this time, the wafer W is heated and the temperature of the wafer W is set to 100 ℃, and the temperature of the atmosphere (the temperature inside the constant temperature and humidity chamber) is set to 55 ℃ to 75 ℃.
Fig. 5 is a graph showing the number of residual fluorine atoms when the moisture content of the atmosphere to which the wafer is exposed is changed.
As shown in fig. 5, it can be confirmed that: even when the wafer W is heated, the moisture content of the atmosphere is 67.7g/m3Hereinafter, the amount of the moisture in the atmosphere is 88.5g/m without decreasing the number of the residual fluorine atoms to the standard level of the number of the residual fluorine atoms3In the above, the number of residual fluorine atoms is also reduced to the reference level of the number of residual fluorine atoms.
Further, it is considered that: as a result of heating the wafer W, even when moisture is less likely to adhere to the surface of the wafer W, hydrogen and fluorine on the surface of the wafer W are bonded and fluorine terminating silicon is replaced with hydroxyl groups as long as the time for exposing the wafer W to the atmosphere is secured, and therefore, the inventors of the present invention summarized the measurement of the number of residual fluorine atoms when the time for exposing the wafer W to the atmosphere after the COR treatment and the PHT treatment is changed in the graph of fig. 6. At this time, the wafer W was heated and the temperature of the wafer W was set to 100 ℃, the temperature of the atmosphere (the temperature inside the constant temperature and humidity chamber) was set to 55 ℃, and the moisture content in the atmosphere was set to 88.5g/m3。
Fig. 6 is a graph showing the number of residual fluorine atoms when the wafer is exposed to the high-humidity atmosphere for a varying period of time.
As shown in fig. 6, it can be confirmed that: even when the wafer W is heated, the number of residual fluorine atoms is reduced to the reference residual fluorine atom number level as long as the wafer W is exposed to the atmosphere for at least 3 minutes. In addition, in the above-described experiment in which the wafer W is stored in the constant temperature and humidity chamber, since it takes two minutes for the temperature and the moisture content inside the constant temperature and humidity chamber to reach the set conditions after the wafer W is stored in the constant temperature and humidity chamber, the substantial time during which the wafer W is exposed to the high-humidity atmosphere in the constant temperature and humidity chamber becomes the time obtained by subtracting two minutes from the time indicated by the horizontal axis of the graph of fig. 6.
The present invention is based on the above findings.
Fig. 7 is a flowchart showing an oxide film removal process as a substrate processing method of the present embodiment.
In fig. 7, first, in one process module 13, COR processing is performed on a wafer W (step S71) (step 1). Specifically, after the wafer W is placed on the stage 15 disposed inside one process module 13, a process gas containing a hydrogen fluoride gas, an argon gas, an ammonia gas, and a nitrogen gas is introduced into the process module 13, and an oxide film formed on the surface of the wafer W, for example, a silicon oxide film, is reacted with the hydrogen fluoride gas and the ammonia gas, thereby generating Ammonium Fluorosilicate (AFS) as a reaction product from the oxide film.
Next, the PHT process is performed on the wafer W in another process module 13 (step S72). Specifically, the wafer W subjected to the COR process is taken out from one process module 13 by the transfer arm 14, placed on the stage 15 disposed inside the other process module 13, and the wafer W placed thereon is heated by a heater or the like incorporated in the stage 15. At this time, the temperature of the wafer W is increased to, for example, about 120 ℃, and AFS generated on the wafer W is decomposed and sublimated due to heat. However, as shown in fig. 4 (a), fluorine alone is present on the surface of the wafer W after AFS sublimation, and silicon exposed on the surface of the wafer W by removal of the oxide film is terminated with fluorine.
Next, the wafer W is exposed to a high-humidity atmosphere in the refrigerating unit 20 (step S73). Specifically, the wafer W subjected to the PHT process is taken out from the other process module 13 by the transfer arm 14, is transferred to the refrigerating unit 20 via the load lock module 19 and the load module 18, and is placed on the stage 32. Then, the device is built in a stageThe heater 33 and the cooling passage 34 of the heater 32 adjust the temperature of the wafer W placed thereon. For example, the temperature of the wafer W is lowered from about 120 ℃ to maintain it at 10 to 80 ℃, more preferably 24 to 60 ℃, and the humidity is adjusted by the moisture supply mechanism 29 and the inert gas supply mechanism 30 so that the moisture content in the processing chamber 28 becomes 50g/m3The above. At this time, the water exposure amount of the wafer W was 50g/m3The atmosphere described above is maintained for a predetermined time, for example, 10 minutes or longer (step 2). Alternatively, for example, the temperature of the wafer W is lowered from about 120 ℃ so as to be higher than the temperature inside the processing chamber 28 and set to be within 50 ℃ of the difference with the temperature inside the processing chamber 28, specifically, so that the temperature of the wafer W is 100 ℃, and the humidity is adjusted so that the moisture content inside the processing chamber 28 becomes 88.5g/m3The above. At this time, the wafer W was exposed to water in an amount of 88.5g/m3The above atmosphere was maintained for at least 3 minutes (2 nd step). As shown in fig. 4 (C), the fluorine of the monomer present on the surface of the wafer W is combined with hydrogen to become hydrogen fluoride, and sublimated. Fluorine that blocks silicon on the surface of the wafer W is replaced with hydrogen or hydroxyl. The sublimated hydrogen fluoride and the replaced fluorine are exhausted from the inside of the processing chamber 28 by the exhaust mechanism 31. The predetermined time is determined by the environment inside the processing chamber 28 of the refrigerating unit 20, particularly the moisture amount, and therefore, is not limited to the above-mentioned 10 minutes or more, and for example, if the moisture amount is more than 50g/m3The predetermined time may be less than 10 minutes.
Thereafter, the wafer W is taken out from the refrigerating portion 20, and the wafer W is output to the foup 16 via the load module 18, and the process is ended.
According to the process shown in FIG. 7, the wafer W subjected to the COR process and the PHT process is exposed to a humidity adjusted moisture content of 50g/m3The above atmosphere. Alternatively, the wafer W subjected to the COR process and the PHT process is set to have a temperature higher than the temperature inside the processing chamber 28 and a temperature difference with the temperature inside the processing chamber 28 of 50 ℃ or less, and the exposure to humidity is adjusted so that the moisture content contained in the wafer W becomes 88.5g/m3The above atmosphere. At this time, the wafer W is present on the surfaceFluorine in the monomer is combined with hydrogen in the moisture to be hydrogen fluoride, and the hydrogen fluoride is sublimated and removed. Fluorine that blocks silicon on the surface of the wafer W is replaced with hydrogen and hydroxyl in the water and removed. That is, since fluorine can be removed from the wafer W only by exposure to the atmosphere whose humidity is adjusted to a high value, a mechanism or a process for generating plasma for removing fluorine is not necessary. As a result, the residual fluorine can be removed with a simple structure without lowering the productivity.
In the above-described processing of fig. 7, as shown in fig. 4 (D), silicon on the surface of the wafer W is terminated with hydrogen and hydroxyl groups and stabilized. This can suppress the oxide film from increasing again after the treatment of fig. 7. In general, in order to prevent the oxide film from being regenerated by natural oxidation after the oxide film removal process is performed on the wafer, it is necessary to manage, specifically, shorten the time from the oxide film removal process to the next process. On the other hand, in the process of fig. 7, as described above, since the oxide film can be prevented from increasing again after the process of fig. 7, it is possible to eliminate the need to manage the time from the process of fig. 7 to the next process, and it is possible to reduce the load on the user of the substrate processing system 10.
In the process shown in fig. 7, residual fluorine is removed while the wafer W is cooled in the refrigerating unit 20. This eliminates the need to separate the cooling step of the wafer W and the residual fluorine removal step, and thus can reliably prevent a reduction in productivity.
In the above-described processing of fig. 7, in the refrigerating unit 20, the adjustment of the moisture amount in the processing chamber 28 and the discharge of the atmosphere in the processing chamber 28 may be repeated by the moisture supply mechanism 29 and the inert gas supply mechanism 30 and the discharge of the atmosphere in the processing chamber 28 may be repeated by the gas discharge mechanism 31. This makes it possible to remove hydrogen fluoride sublimated from the surface of the wafer W and fluorine replaced therewith extremely quickly, and to maintain the fluorine concentration on the surface of the wafer W at an extremely low level. As a result, the possibility that the replaced fluorine remains on the surface of the wafer W again or that fluorine in the hydrogen fluoride ends up silicon again can be reduced.
In the process of fig. 7, the wafer W subjected to the COR process and the PHT process is exposed to an atmosphere containing moisture, but the atmosphere may contain a hydroxyl group or hydrogen, and for example, the same effects as those of the present embodiment can be obtained even when the wafer W is exposed to an atmosphere containing an alcohol containing a hydroxyl group or hydrogen, such as ethanol, methanol, propanol, or butanol. Further, since there is a possibility that moisture adheres to the surface of the wafer W exposed to the atmosphere containing moisture and remains without being evaporated, the wafer W from which residual fluorine has been removed by the process of fig. 7 may be dried by a drying module or the like provided in the substrate processing system 10 or independently.
In the above-described process of fig. 7, the residual fluorine on the wafer W is removed in the refrigerating unit 20 provided in the substrate processing system 10, but the refrigerating unit 20 may be provided separately from the substrate processing system 10, and the residual fluorine on the wafer W may be removed by exposing the wafer W to a high-humidity atmosphere in the refrigerating unit 20 provided separately. In the process of fig. 7, after the PHT process is performed on the wafer W, the wafer W may be transported to the foup 16 without being transported to the refrigerating unit 20, and the residual fluorine may be removed from the wafer W by adjusting the humidity and temperature inside the foup 16.
In the process of fig. 7, the COR process is performed as a process using a fluorine-containing gas, but the process using a fluorine-containing gas is not limited to the COR process, and may be a process using a fluorine plasma generated from a fluorine-containing gas, for example, and the process may be not limited to a film removal process, an etching process, or a film formation process. In any of the processes, residual fluorine can be removed by exposing the wafer W to a high-humidity atmosphere while adjusting the temperature of the wafer W in the refrigerating unit 20.
The embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments.
The object of the present invention can also be achieved by supplying a storage medium, in which program codes of software for realizing the functions of the above-described embodiments are stored, to the controller 27 provided in the substrate processing system 10, and reading and executing the program codes stored in the storage medium by the CPU of the controller 27.
In this case, the program code itself read from the storage medium realizes the functions of the above-described embodiments, and the program code and the storage medium storing the program code constitute the present invention.
The storage medium for supplying the program code may be any storage medium capable of storing the program code, such as an optical disk, e.g., a RAM, NV-RAM, a flexible disk (フロッピー (registered trademark of flopy) ディスク), a hard disk, an optical disk, a CD-ROM, CD-R, CD-RW, or a DVD (DVD-ROM, DVD-RW, or DVD + RW), a magnetic tape, a nonvolatile memory card, or another ROM. Alternatively, the program code may be downloaded from another computer, a database, or the like, not shown, connected to the internet, a commercial network, a local area network, or the like, and supplied to the controller 27.
In addition, not only the case where the controller 27 implements the functions of the above-described embodiment by executing the read program codes but also the case where: an OS (operating system) or the like operating on the CPU based on the instruction of the program code performs a part or all of the actual processing, and the functions of the above-described embodiments are realized by this processing.
Further, the following is also included: the program code read from the storage medium is written into a memory included in a function expansion board inserted into the controller 27 or a function expansion unit connected to the controller 27, and then based on an instruction of the program code, a CPU or the like included in the function expansion board or the function expansion unit performs a part or all of actual processing, and the functions of the above-described embodiments can be realized by the processing.
The program code may be in the form of object code, program code executable by a translator, script data suppliable to an OS, or the like.

Claims (11)

1. A method for processing a substrate, characterized in that,
the substrate processing method comprises a 1 st step of performing a process using a fluorine-containing gas on a substrate and a 2 nd step of exposing the substrate to an atmosphere containing moisture,
the atmosphere contains water in an amount of 50g/m3In the above-mentioned manner,
in the 2 nd step, the temperature of the substrate is set so that a difference from the temperature of the atmosphere is within 50 ℃,
the 2 nd step of exposing the substrate to an atmosphere containing moisture is performed in an atmospheric pressure atmosphere.
2. The substrate processing method according to claim 1,
in the 2 nd step, the substrate is exposed to the atmosphere for a predetermined time.
3. The substrate processing method according to claim 1,
in the 2 nd step, the temperature of the substrate is maintained at 10 to 80 ℃.
4. The substrate processing method according to claim 3,
in the 2 nd step, the temperature of the substrate is maintained at 24 to 60 ℃.
5. The substrate processing method according to claim 1,
in the 2 nd step, the temperature of the substrate is set to be higher than the temperature of the atmosphere.
6. The substrate processing method according to claim 5,
the amount of moisture contained in the atmosphere was 88.5g/m3The above.
7. The substrate processing method according to claim 6,
in the 2 nd step, the substrate is exposed to the atmosphere for at least 3 minutes.
8. The substrate processing method according to any one of claims 1 to 7,
the treatment using a fluorine-containing gas is a COR treatment.
9. The substrate processing method according to any one of claims 1 to 7,
the treatment using the fluorine-containing gas is a treatment using a fluorine plasma generated from the gas.
10. A substrate processing apparatus is characterized in that,
the substrate processing apparatus includes:
a processing chamber for accommodating a substrate subjected to a process using a fluorine-containing gas;
a moisture containing mechanism for containing moisture in an atmosphere in the processing chamber,
the moisture-containing mechanism sets the amount of moisture contained in the atmosphere to 50g/m3In the above-mentioned manner,
the temperature of the substrate is set so that the difference between the temperature of the substrate and the temperature of the atmosphere is within 50 ℃,
the moisture containing mechanism makes the atmosphere in the processing chamber contain moisture in an atmospheric pressure atmosphere.
11. A substrate processing system, comprising a substrate processing apparatus,
the substrate processing system includes:
a substrate processing apparatus that performs a process using a gas containing fluorine on a substrate;
a post-treatment apparatus for exposing the substrate subjected to the treatment using the fluorine-containing gas to an atmosphere containing moisture,
the atmosphere contains water in an amount of 50g/m3In the above-mentioned manner,
the temperature of the substrate is set so that the difference between the temperature of the substrate and the temperature of the atmosphere is within 50 ℃,
the post-processing apparatus exposes the substrate subjected to the processing using the fluorine-containing gas to an atmosphere containing moisture in an atmospheric pressure atmosphere.
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