CN116741674A - Substrate processing method, substrate processing apparatus, and pre-drying treatment liquid - Google Patents
Substrate processing method, substrate processing apparatus, and pre-drying treatment liquid Download PDFInfo
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- CN116741674A CN116741674A CN202310947663.3A CN202310947663A CN116741674A CN 116741674 A CN116741674 A CN 116741674A CN 202310947663 A CN202310947663 A CN 202310947663A CN 116741674 A CN116741674 A CN 116741674A
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- 238000012545 processing Methods 0.000 title abstract description 121
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- 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
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67028—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
- H01L21/67034—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for drying
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
The application relates to a substrate processing method, a substrate processing apparatus and a pre-drying treatment liquid. A pre-drying treatment liquid is supplied to the surface of the substrate on which the pattern is formed, wherein the pre-drying treatment liquid is a solution containing a sublimate substance which is changed into a gas without passing through the liquid and a solvent which is mutually soluble with the sublimate substance. Then, the solvent is evaporated from the pre-drying treatment liquid on the surface of the substrate, thereby forming a solidified body containing the sublimating substance on the surface of the substrate. The solidified body is then removed from the surface of the substrate by sublimating the solidified body. The ratio of the thickness of the solidified body to the height of the pattern multiplied by one hundred has a value exceeding 76 and less than 219.
Description
The application relates to a method for processing a substrate, a substrate processing device and a Chinese patent application No.201910544595.X of the prior drying treatment liquid, which is filed on the application date of 2019, 6 and 21 days
Cross Reference to Related Applications
The present application claims priority based on japanese patent application No. 2018-119092, filed on 22 th month 2018, and japanese patent application No. 2019-050214, filed on 18 th month 2019, the entire contents of which are incorporated herein by reference.
Technical Field
The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate, and a pre-drying treatment liquid to be supplied to a surface of a substrate before drying the surface of the substrate. Substrates to be processed include, for example, substrates for FPDs (Flat Panel Display) such as semiconductor wafers, liquid crystal display devices, organic EL (electroluminescence) display devices, substrates for optical discs, substrates for magnetic discs, substrates for magneto-optical discs, substrates for photomasks, ceramic substrates, substrates for solar cells, and the like.
Background
In a process for manufacturing a semiconductor device, a liquid crystal display device, or the like, a substrate such as a semiconductor wafer or a glass substrate for a liquid crystal display device is subjected to processing as necessary. Such treatment includes supplying a treatment liquid such as a chemical liquid or a rinse liquid to the substrate. After the treatment liquid is supplied, the treatment liquid is removed from the substrate, and the substrate is dried. In a monolithic substrate processing apparatus that processes substrates one by one, the following spin drying is performed: the liquid attached to the substrate is removed by high-speed rotation of the substrate, thereby drying the substrate.
When the substrate is dried with a pattern formed on the surface of the substrate, there are cases where: a force caused by the surface tension of the processing liquid attached to the substrate is applied to the pattern, and the pattern collapses. As a countermeasure therefor, the following method is adopted: a liquid having a low surface tension such as IPA (isopropyl alcohol) is supplied to the substrate, or a hydrophobizing agent which brings the contact angle of the liquid with the pattern close to 90 degrees is supplied to the substrate. However, even if IPA or a hydrophobizing agent is used, the collapse force for collapsing the pattern cannot be zero, and therefore, depending on the strength of the pattern, collapse of the pattern cannot be sufficiently prevented even if these measures are implemented in some cases.
In recent years, sublimation drying has received attention as a technique for preventing pattern collapse. A substrate processing method and a substrate processing apparatus for performing sublimation drying are disclosed in, for example, JP 2012-243869A. In the sublimation drying described in JP 2012-243869A, a solution of a sublimation substance is supplied to the upper surface of a substrate, and DIW on the substrate is replaced with the solution of the sublimation substance. Then, the solvent of the sublimating substance is dried, thereby precipitating the sublimating substance. Thereby, a film formed of a sublimating substance in a solid state is formed on the upper surface of the substrate. In paragraph 0028 of JP 2012-243869A, the following is described: the "film thickness" t of the film made of the sublimating substance "is preferably as thin as possible as long as the convex portion 101 of the pattern is sufficiently covered. ". After the film formed of the sublimating substance in a solid state is formed, the substrate is heated. Thereby, the sublimating substance on the substrate sublimates and is removed from the substrate.
Disclosure of Invention
Generally, the pattern collapse rate of sublimation drying is lower than conventional drying methods such as spin drying in which liquid is removed by high-speed rotation of a substrate and IPA drying using IPA. However, if the strength of the pattern is extremely low, the pattern may not be sufficiently prevented from collapsing even if sublimation drying is performed. As a result of studies by the inventors of the present application, it was found that one of the reasons for this is the thickness of the solidified material containing the sublimate. In JP 2012-243869A, only "the film thickness" t "of the film formed of the sublimating substance is required to sufficiently cover the convex portion 101 of the pattern, and it is preferable to be as thin as possible. The "description is not made with respect to the thickness of the film formed of the sublimating substance sufficiently.
An object of the present invention is to provide a substrate processing method, a substrate processing apparatus, and a pre-drying processing liquid, which can reduce pattern collapse generated when a substrate is dried by sublimation drying.
One embodiment of the present invention provides a substrate processing method including the steps of: a pre-drying treatment liquid supply step of supplying a pre-drying treatment liquid, which is a solution containing a sublimate substance that changes to a gas without passing through a liquid and a solvent that is mutually soluble in the sublimate substance, to a surface of a substrate on which a pattern is formed; a solidification body formation step of forming a solidification body containing the sublimating substance on the surface of the substrate by evaporating the solvent from the pre-drying treatment liquid on the surface of the substrate; and a sublimation step of removing the solidified material from the surface of the substrate by sublimating the solidified material, wherein the ratio of the thickness of the solidified material to the height of the pattern in the substrate processing method is more than 76 and less than 219.
According to this method, a pre-drying treatment liquid containing a sublimate corresponding to a solute and a solvent is supplied to the surface of the patterned substrate. Then, the solvent was evaporated from the pre-drying treatment liquid. Thereby, a solidified body containing a sublimating substance is formed on the surface of the substrate. Then, the solidified material on the substrate is changed into a gas without passing through the liquid. Thereby, the solidified body is removed from the surface of the substrate. Therefore, the collapse rate of the pattern can be reduced as compared with conventional drying methods such as spin drying.
When the solvent is evaporated from the drying pretreatment liquid, a solidified material containing a sublimating substance is formed on the surface of the substrate. When a value obtained by multiplying the ratio of the thickness of the solidified body to the height of the pattern by one hundred is defined as the embedding rate, the embedding rate at the point in time when the solidified body is formed exceeds 76 and is less than 219. When the embedding rate is outside this range, the number of collapse of the pattern increases according to the strength of the pattern. In contrast, when the embedding rate is within this range, the number of collapse of the pattern can be reduced even if the strength of the pattern is low. Therefore, even if the strength of the pattern is low, the collapse rate of the pattern can be reduced.
In the above embodiment, at least one of the following features may be added to the above substrate processing method.
The sublimating substance contains at least one of camphor and naphthalene.
The solvent includes at least one of IPA (isopropyl alcohol), acetone, and PGEE (propylene glycol monoethyl ether).
The solvent is IPA, and the mass percentage concentration of the sublimate in the drying pretreatment liquid exceeds 0.62 and is less than 2.06.
The solvent is acetone, and the concentration of the sublimating substance in the drying pretreatment liquid exceeds 0.62 and is less than 0.96 by mass.
The solvent is PGEE, and the concentration of the sublimating substance in the pre-drying treatment liquid exceeds 3.55 and is less than 6.86.
The pretreatment liquid for drying to be supplied to the surface of the substrate in the pretreatment liquid for drying supplying step is a solution containing: the above-mentioned sublimating substance containing a hydrophobic group; the above solvent; and an adsorbent substance which contains a hydrophobic group and a hydrophilic group and has a higher hydrophilicity than the sublimating substance.
According to this method, a pre-drying treatment liquid containing an adsorption substance in addition to a sublimating substance and a solvent is supplied to the surface of the patterned substrate. Then, the solvent was evaporated from the pre-drying treatment liquid. Thereby, a solidified body containing a sublimating substance is formed on the surface of the substrate. Then, the solidified material on the substrate is changed into a gas without passing through the liquid. Thereby, the solidified body is removed from the surface of the substrate. Therefore, the collapse rate of the pattern can be reduced as compared with conventional drying methods such as spin drying.
The sublimating substance is a substance containing a hydrophobic group in a molecule. The adsorption material is a material containing a hydrophobic group and a hydrophilic group in a molecule. The hydrophilic nature of the adsorbed material is higher than the hydrophilic nature of the sublimating material. When the surface of the pattern is either hydrophilic or hydrophobic, or the surface of the pattern includes a hydrophilic portion and a hydrophobic portion, the adsorbing substance in the pretreatment liquid before drying is adsorbed on the surface of the pattern.
Specifically, when the surface of the pattern is hydrophilic, hydrophilic groups of the adsorbed substance in the pretreatment liquid adhere to the surface of the pattern, and hydrophobic groups of the sublimated substance in the pretreatment liquid adhere to the hydrophobic groups of the adsorbed substance. Thereby, the sublimating substance is held on the surface of the pattern through the adsorption substance. When the surface of the pattern is hydrophobic, at least a hydrophobic group of the sublimating substance adheres to the surface of the pattern. Therefore, when the surface of the pattern is either hydrophilic or hydrophobic, or the surface of the pattern includes a hydrophilic portion and a hydrophobic portion, the sublimating substance is held on or near the surface of the pattern before the solvent evaporates.
When the sublimating substance is hydrophilic and the surface of the pattern is hydrophilic, the sublimating substance is attracted to the surface of the pattern by electrostatic attraction. On the other hand, when the sublimating substance is hydrophobic and the surface of the pattern is hydrophilic, such attractive force is weak or does not occur, and therefore, the sublimating substance is difficult to adhere to the surface of the pattern. In addition, when the sublimating substance is hydrophobic, the surface of the pattern is hydrophilic, and the space between the patterns is extremely narrow, it is considered that a sufficient amount of sublimating substance does not enter between the patterns. These phenomena occur also when the sublimating substance is hydrophilic and the surface of the pattern is hydrophobic.
When the solvent is evaporated in a state where the surface of the pattern or the vicinity thereof is free from the sublimating substance, a collapsing force is applied to the pattern from the solvent in contact with the surface of the pattern, and the pattern may collapse. It is also considered that when the solvent is evaporated in a state where there is no sufficient amount of the sublimating substance between the patterns, the gaps between the patterns are not buried by the solidified material, and the patterns collapse. If the sublimating substance is disposed on or near the surface of the pattern before the solvent is evaporated, such collapse can be reduced. This can reduce the collapse rate of the pattern.
The hydrophilic group can be hydroxyl group (hydroxyl group), carboxyl group (COOH), amino group (NH) 2 ) Any one of Carbonyl (CO)Groups other than these may be used. The hydrophobic group may be a hydrocarbon group, an alkyl group (C n H 2n+1 ) Cycloalkyl (C) n H 2n+1 ) Phenyl (C) 6 H 5 ) Any of them may be other groups.
The adsorption substance is a substance having sublimability.
According to this method, not only the sublimation material but also the adsorption material is sublimated. The adsorptive substance changes from solid to gas at normal temperature or normal pressure without passing through liquid. When at least a part of the surface of the pattern is hydrophilic, the solvent evaporates in a state where the adsorbing substance in the treatment liquid is adsorbed on the surface of the pattern before drying. The adsorbed species change from liquid to solid at the surface of the pattern. Thereby, a solidified body containing the adsorbed substance and the sublimating substance is formed. Then, the solid of the adsorbed substance is changed to a gas without passing through a liquid on the surface of the pattern. Therefore, the collapse force can be reduced as compared with the case where the liquid is vaporized on the surface of the pattern.
The concentration of the adsorbent in the pre-drying treatment liquid is lower than the concentration of the solvent in the pre-drying treatment liquid.
According to this method, a pretreatment liquid for drying having a low concentration of an adsorbed substance is supplied to the surface of the substrate. When at least a part of the surface of the pattern is hydrophilic, hydrophilic groups of the adsorbed substance adhere to the surface of the pattern, and a monomolecular film of the adsorbed substance is formed along the surface of the pattern. When the concentration of the adsorbed substance is high, a plurality of monomolecular films are stacked to form a laminated film of the adsorbed substance along the surface of the pattern. In this case, the sublimating substance is held on the surface of the pattern through the laminated film of the adsorbing substance. When the laminated film of the adsorbed substance is thick, the sublimating substance entering between the patterns is reduced. Therefore, by reducing the concentration of the adsorbed substance, more sublimating substance can be made to enter between the patterns.
When at least a part of the surface of the pattern is hydrophilic, the concentration of the adsorbed substance in the pretreatment liquid before drying may be a value at or above which a monomolecular film of the adsorbed substance is formed on the surface of the pattern. In the former case, the sublimating substance is held on the surface of the pattern through a monomolecular film of the adsorbing substance. Therefore, even if at least a part of the surface of the pattern is hydrophilic, the sublimating substance can be disposed in the vicinity of the surface of the pattern. Further, since only the thinnest monolayer of the adsorbed substance is interposed between the sublimating substance and the pattern, a sufficient amount of the sublimating substance can be allowed to enter between the patterns.
The sublimating substance has a higher hydrophobicity than the adsorbing substance. The solubility of the sublimating substance in the oil is higher than the solubility of the adsorbing substance in the oil. In other words, the solubility of the sublimating substance in water is lower than the solubility of the adsorbing substance in water.
According to this method, a pre-drying treatment liquid containing a sublimating substance having a higher hydrophobicity than the adsorbed substance is supplied to the surface of the substrate. Since both the sublimation material and the adsorption material contain hydrophobic groups, both the sublimation material and the adsorption material can be attached to the surface of the pattern in the case where at least a portion of the surface of the pattern is hydrophobic. However, since the affinity of the sublimating substance with the pattern is higher than the affinity of the adsorbing substance with the pattern, more sublimating substance adheres to the surface of the pattern than the adsorbing substance. This allows more sublimating substances to adhere to the surface of the pattern.
Other embodiments of the present invention provide a substrate processing apparatus comprising: a pre-drying treatment liquid supply unit that supplies a pre-drying treatment liquid, which is a solution containing a sublimate substance that changes to a gas without passing through a liquid and a solvent that is mutually soluble in the sublimate substance, to a surface of a substrate on which a pattern is formed; a solidification body forming unit that forms a solidification body containing the sublimating substance on a surface of the substrate by evaporating the solvent from the pre-drying treatment liquid on the surface of the substrate; and a sublimation unit that sublimates the solidified material to remove the solidified material from the surface of the substrate, wherein a ratio of a thickness of the solidified material to a height of the pattern in the substrate processing apparatus is more than 76 and less than 219. With the above configuration, the same effects as those of the substrate processing method described above can be obtained.
Another embodiment of the present application provides a pretreatment liquid for drying, which is a pretreatment liquid for drying a surface of a substrate on which a pattern is formed, the pretreatment liquid including a sublimate which changes to a gas without passing through a liquid, and a solvent which is compatible with the sublimate, wherein a concentration of the sublimate is adjusted so that a value obtained by multiplying a ratio of a thickness of the sublimate to a height of the pattern by one hundred exceeds 76 and is smaller than 219 when the solvent is evaporated from the pretreatment liquid for drying on the surface of the substrate, thereby forming a solidified body including the sublimate on the surface of the substrate. With the above configuration, the same effects as those of the substrate processing method described above can be obtained.
The application relates to the following:
the substrate processing method according to item 1, comprising:
a pre-drying treatment liquid supply step of supplying a pre-drying treatment liquid, which is a solution containing a sublimate substance that changes to a gas without passing through a liquid and a solvent that is mutually soluble in the sublimate substance, to a surface of a substrate on which a pattern is formed;
A solidification body formation step of forming a solidification body containing the sublimating substance on the surface of the substrate by evaporating the solvent from the pre-drying treatment liquid on the surface of the substrate; and
a sublimation step of removing the solidified material from the surface of the substrate by sublimating the solidified material,
the ratio of the thickness of the solidified body to the height of the pattern multiplied by one hundred has a value exceeding 76 and less than 219.
The substrate processing method according to item 2, wherein the sublimating substance contains at least one of camphor and naphthalene.
The substrate processing method according to item 3, wherein the solvent comprises at least one of IPA (isopropyl alcohol), acetone, and PGEE (propylene glycol monoethyl ether).
Item 4, the substrate processing method of item 3, wherein,
the solvent is IPA,
the mass percentage concentration of the sublimating substances in the drying pretreatment liquid exceeds 0.62 and is less than 2.06.
Item 5, the substrate processing method of item 3, wherein,
the solvent is acetone, and the solvent is acetone,
the concentration of the sublimating substance in the pretreatment liquid exceeds 0.62 and is not more than 0.96 by mass.
Item 6, the substrate processing method of item 3, wherein,
the solvent is PGEE,
the concentration of the sublimating substance in the pretreatment liquid exceeds 3.55 and is less than 6.86 by mass.
The substrate processing method according to item 7, wherein the pretreatment liquid to be supplied to the surface of the substrate in the pretreatment liquid supply step is a solution containing: the sublimating substance containing a hydrophobic group; the solvent; and an adsorbent substance having a hydrophobic group and a hydrophilic group and having a higher hydrophilicity than the sublimating substance.
The substrate processing method according to item 8, wherein the adsorption substance is a substance having sublimation property.
The substrate processing method according to item 9, wherein the concentration of the adsorbing substance in the pre-drying treatment liquid is lower than the concentration of the solvent in the pre-drying treatment liquid.
The substrate processing method according to item 10, wherein the sublimating substance has a higher hydrophobicity than the adsorbing substance.
Item 11, substrate processing apparatus comprising the unit of:
a pre-drying treatment liquid supply unit that supplies a pre-drying treatment liquid, which is a solution containing a sublimate substance that changes to a gas without passing through a liquid and a solvent that is mutually soluble in the sublimate substance, to a surface of a substrate on which a pattern is formed;
A solidification body forming unit that forms a solidification body containing the sublimating substance on a surface of the substrate by evaporating the solvent from the pre-drying treatment liquid on the surface of the substrate; and
a sublimation unit that sublimates the solidified body to remove the solidified body from the surface of the substrate,
the ratio of the thickness of the solidified body to the height of the pattern multiplied by one hundred has a value exceeding 76 and less than 219.
Item 12, drying pretreatment liquid, which is a drying pretreatment liquid supplied to the surface of a substrate on which a pattern is formed before drying the surface of the substrate,
the pretreatment liquid for drying comprises:
sublimating substances which are changed into gases without liquid; and
a solvent miscible with the sublimating substance,
the concentration of the sublimating substance is adjusted so that a value obtained by multiplying a ratio of a thickness of the condensed body with respect to a height of the pattern by one hundred exceeds 76 and is less than 219 when the condensed body containing the sublimating substance is formed on the surface of the substrate by evaporating the solvent from the drying pretreatment liquid on the surface of the substrate.
The above and other objects, features and effects of the present invention will be apparent from the following description of the embodiments with reference to the accompanying drawings.
Drawings
Fig. 1A is a schematic view of a substrate processing apparatus according to embodiment 1 of the present invention as viewed from above.
Fig. 1B is a schematic view of the substrate processing apparatus as seen from the side.
Fig. 2 is a schematic view of the inside of a processing unit provided in the substrate processing apparatus, viewed horizontally.
Fig. 3 is a schematic view showing a pretreatment-drying treatment liquid supply unit provided in the substrate processing apparatus.
Fig. 4 is a block diagram showing hardware of the control device.
Fig. 5 is a process diagram for explaining an example of substrate processing according to embodiment 1.
Fig. 6A is a schematic view showing a state of a substrate when the substrate process shown in fig. 5 is performed.
Fig. 6B is a schematic view showing a state of the substrate when the substrate process shown in fig. 5 is performed.
Fig. 6C is a schematic view showing a state of the substrate when the substrate process shown in fig. 5 is performed.
Fig. 7 is a graph showing an example of an image (image) in which the thickness of a liquid film of a pre-drying treatment liquid on a substrate is reduced by evaporation of a solvent.
Fig. 8 is a graph showing an example of the relationship between the initial concentration of the sublimate and the thickness of the solidified body.
Fig. 9 is a table showing an example of the embedding rate and the collapse rate of the pattern obtained when a plurality of samples having patterns of the same shape and strength formed thereon are treated while changing the initial concentration of camphor.
Fig. 10 is a line graph showing a relationship between the concentration of camphor and the collapse rate of the pattern in fig. 9.
Fig. 11 is a line graph showing a relationship between the embedding rate and the collapse rate of the pattern in fig. 9.
Fig. 12A and 12B are schematic diagrams for explaining a mechanism assumed for a phenomenon that the collapse rate of the pattern becomes high when the solidified body is excessively thick.
Fig. 13A and 13B are schematic diagrams for explaining a mechanism assumed for a phenomenon that the collapse rate of the pattern becomes high when the solidified body is excessively thin.
Fig. 14 is a table showing an example of the collapse rate of a pattern obtained when a plurality of samples on which patterns having the same shape and strength are formed are treated while changing the initial concentration of camphor.
Fig. 15 is a table showing an example of the collapse rate of a pattern obtained when a plurality of samples on which patterns having the same shape and strength are formed are treated while changing the initial concentration of camphor.
Fig. 16 is a table showing an example of the collapse rate of a pattern obtained when a plurality of samples on which patterns having the same shape and strength are formed are treated while changing the initial concentration of camphor.
Fig. 17 is a line graph showing a relationship between the concentration of camphor and the collapse rate of the pattern in fig. 14.
Fig. 18 is a line graph showing a relationship between the concentration of camphor and the collapse rate of the pattern in fig. 15.
Fig. 19 is a line graph showing a relationship between the concentration of camphor and the collapse rate of the pattern in fig. 16.
Fig. 20 is a graph obtained by overlapping the folding lines of fig. 17 to 19.
Fig. 21 is a schematic view of the inside of a processing unit included in the substrate processing apparatus according to embodiment 2.
Fig. 22 is a process diagram for explaining an example of substrate processing according to embodiment 2.
Fig. 23A is a cross-sectional view of a substrate for explaining a phenomenon that is supposed to occur at the surface of the pattern to which the pre-drying treatment liquid is supplied.
Fig. 23B is a cross-sectional view of a substrate for explaining the same phenomenon.
Fig. 23C is a cross-sectional view of a substrate for explaining the same phenomenon.
Fig. 23D is a cross-sectional view of a substrate for explaining the same phenomenon.
Fig. 23E is a cross-sectional view of a substrate for explaining the same phenomenon.
Fig. 23F is a cross-sectional view of a substrate for explaining the same phenomenon.
Detailed Description
In the following description, unless otherwise specified, the air pressure in the substrate processing apparatus 1 is maintained at the air pressure (for example, a value of 1 atmosphere or the vicinity thereof) in the clean room where the substrate processing apparatus 1 is installed.
Fig. 1A is a schematic view of a substrate processing apparatus 1 according to embodiment 1 of the present invention as viewed from above. Fig. 1B is a schematic view of the substrate processing apparatus 1 as seen from the side.
As shown in fig. 1A, the substrate processing apparatus 1 is a monolithic apparatus for processing a disk-shaped substrate W such as a semiconductor wafer one by one. The substrate processing apparatus 1 includes: a Load Port (LP) for holding a carrier C for accommodating a substrate W; a plurality of processing units 2 for processing the substrates W transferred from the carriers C on the load port LP with a processing fluid such as a processing liquid or a processing gas; a transfer robot for transferring a substrate W between a carrier C on a load port LP and a processing unit 2; and a control device 3 for controlling the substrate processing apparatus 1.
The carrying manipulator comprises: an Indexer Robot (IR) for carrying in and carrying out the substrate W with respect to the carrier C on the load port LP; and a Center Robot (CR) for carrying in and out the substrate W with respect to the plurality of processing units 2. The indexer robot IR transports the substrate W between the load port LP and the central robot CR, which transports the substrate W between the indexer robot IR and the process unit 2. The central robot CR includes a hand H1 supporting the substrate W, and the indexer robot IR includes a hand H2 supporting the substrate W.
The plurality of processing units 2 form a plurality of tower portions TW arranged around the center robot CR in a plan view. Fig. 1A shows an example in which 4 tower portions TW are formed. The center robot CR can enter any tower TW. As shown in fig. 1B, each tower TW includes a plurality of (e.g., 3) process units 2 stacked up and down.
Fig. 2 is a schematic view of the inside of the processing unit 2 included in the substrate processing apparatus 1 viewed horizontally.
The processing unit 2 is a wet processing unit 2W for supplying a processing liquid to the substrate W. The processing unit 2 includes: a box-shaped chamber 4 having an inner space; a spin chuck 10 that rotates around a vertical rotation axis A1 (the rotation axis A1 passes through a central portion of the substrate W) while keeping 1 substrate W horizontal in the chamber 4; and a tubular processing cup 21 surrounding the spin chuck 10 around the rotation axis A1.
The chamber 4 comprises: a box-shaped partition wall 5 provided with a carry-in/out port 5b through which the substrate W passes; and a shutter 7 for opening and closing the carry-in/carry-out port 5 b. The FFU6 (fan filter unit) is disposed above the air supply port 5a (which is provided at the upper portion of the partition wall 5). The FFU6 always supplies clean air (air filtered by the filter) from the air supply port 5a into the chamber 4. The gas in the chamber 4 passes through the exhaust line 8 connected to the bottom of the processing cup 21, and is exhausted from the chamber 4. Thereby, a downward flow of clean air is always formed in the chamber 4. The flow rate of the exhaust gas discharged to the exhaust line 8 is changed according to the opening degree of the exhaust valve 9 disposed in the exhaust line 8.
The spin chuck 10 includes: a disk-shaped rotating base 12 held in a horizontal posture; a plurality of chuck pins 11 which hold the substrate W in a horizontal posture above the spin base 12; a rotation shaft 13 extending downward from a central portion of the rotation base 12; and a rotation motor 14 for rotating the rotation base 12 and the plurality of chuck pins 11 by rotating the rotation shaft 13. The spin chuck 10 is not limited to a chuck having chuck pins 11 in contact with the outer peripheral surface of the substrate W, and may be a vacuum chuck in which the back surface (lower surface) of the substrate W, which is a non-device-forming surface, is attracted to the upper surface 12u of the spin base 12 to hold the substrate W horizontally.
The processing cup 21 includes: a plurality of shields 24 for blocking the processing liquid discharged from the substrate W to the outside; a plurality of cups 23 for receiving the processing liquid guided downward by the plurality of shields 24; and a cylindrical outer wall member 22 surrounding the plurality of shields 24 and the plurality of cups 23. Fig. 2 shows the following examples: there are provided 4 shields 24 and 3 cups 23, the outermost cup 23 being integral with the 3 rd shield 24 from above.
The shield 24 comprises: a cylindrical portion 25 surrounding the spin chuck 10; and an annular top plate portion 26 extending obliquely upward from an upper end portion of the cylindrical portion 25 toward the rotation axis A1. The plurality of top plate portions 26 are vertically overlapped, and the plurality of cylindrical portions 25 are arranged in concentric circles. The annular upper end of the top plate 26 corresponds to the upper end 24u of the shield 24 surrounding the substrate W and the spin base 12 in plan view. The plurality of cups 23 are each disposed below the plurality of cylindrical portions 25. The cup 23 forms an annular liquid receiver that receives the processing liquid directed downward by the shield 24.
The processing unit 2 includes a shield lifting unit 27 that lifts and lowers each of the plurality of shields 24. The shield elevating unit 27 positions the shield 24 at any position from the upper position to the lower position. Fig. 2 shows a state in which 2 shields 24 are arranged at the upper position and the remaining 2 shields 24 are arranged at the lower position. The upper position is a position where the upper end 24u of the shield 24 is disposed above a holding position (a position where the substrate W held by the spin chuck 10 is disposed). The lower position is a position where the upper end 24u of the shield 24 is disposed below the holding position.
At least one shield 24 is disposed at an upper position when the processing liquid is supplied to the rotating substrate W. In this state, when the processing liquid is supplied to the substrate W, the processing liquid supplied to the substrate W is thrown off around the substrate W. The thrown-off processing liquid collides with the inner surface of the shield 24 horizontally opposed to the substrate W, and is guided to the cup 23 corresponding to the shield 24. Thereby, the processing liquid discharged from the substrate W is collected in the processing cup 21.
The processing unit 2 includes a plurality of nozzles that eject a processing liquid toward the substrate W held by the spin chuck 10. The plurality of nozzles comprises: a chemical liquid nozzle 31 for ejecting chemical liquid toward the upper surface of the substrate W; a rinse liquid nozzle 35 for ejecting a rinse liquid toward the upper surface of the substrate W; a pre-drying treatment liquid nozzle 39 for ejecting a pre-drying treatment liquid toward the upper surface of the substrate W; and a replacement liquid nozzle 43 for ejecting the replacement liquid toward the upper surface of the substrate W.
The chemical liquid nozzle 31 may be a scanning nozzle horizontally movable in the chamber 4 or may be a fixed nozzle fixed to the partition wall 5 of the chamber 4. The same applies to the rinse liquid nozzle 35, the pre-drying treatment liquid nozzle 39, and the replacement liquid nozzle 43. Fig. 2 shows the following examples: the chemical liquid nozzle 31, the rinse liquid nozzle 35, the pre-drying treatment liquid nozzle 39, and the replacement liquid nozzle 43 are scanning nozzles, and 4 nozzle moving means corresponding to the 4 nozzles are provided.
The chemical liquid nozzle 31 is connected to a chemical liquid pipe 32 for guiding the chemical liquid to the chemical liquid nozzle 31. When the chemical liquid valve 33 attached to the chemical liquid pipe 32 is opened, the chemical liquid is continuously discharged downward from the discharge port of the chemical liquid nozzle 31. The chemical liquid discharged from the chemical liquid nozzle 31 may be a liquid containing at least one of sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, acetic acid, aqueous ammonia, aqueous hydrogen peroxide, an organic acid (e.g., citric acid, oxalic acid, etc.), an organic base (e.g., TMAH: tetramethylammonium hydroxide, etc.), a surfactant, and an anticorrosive, or may be a liquid other than these.
Although not shown, the chemical liquid valve 33 includes: a valve body provided with an internal flow path through which the chemical liquid flows and an annular valve seat surrounding the internal flow path; a valve element movable relative to the valve seat; and an actuator that moves the valve spool between a closed position (the valve spool is in contact with the valve seat) and an open position (the valve spool is away from the valve seat). The same is true for other valves. The actuator may be a pneumatic actuator or an electric actuator, or may be an actuator other than these. The control device 3 controls the actuator to open and close the chemical liquid valve 33.
The chemical liquid nozzle 31 is connected to a nozzle moving unit 34 that moves the chemical liquid nozzle 31 in at least one of the vertical direction and the horizontal direction. The nozzle moving unit 34 horizontally moves the chemical liquid nozzle 31 between a processing position where the chemical liquid ejected from the chemical liquid nozzle 31 is supplied to the upper surface of the substrate W and a standby position where the chemical liquid nozzle 31 is located around the processing cup 21 in a plan view.
The rinse liquid nozzle 35 is connected to a rinse liquid pipe 36 for guiding the rinse liquid to the rinse liquid nozzle 35. When the rinse liquid valve 37 attached to the rinse liquid pipe 36 is opened, the rinse liquid is continuously discharged downward from the discharge port of the rinse liquid nozzle 35. The rinse liquid discharged from the rinse liquid nozzle 35 is, for example, pure water (deionized water: DIW (Deionized Water)). The rinse liquid may be any of carbonated water, electrolytic ionized water, hydrogen water, ozone water, and hydrochloric acid water having a diluted concentration (for example, about 10 to 100 ppm).
The rinse liquid nozzle 35 is connected to a nozzle moving unit 38 that moves the rinse liquid nozzle 35 in at least one of the vertical direction and the horizontal direction. The nozzle moving unit 38 horizontally moves the rinse liquid nozzle 35 between a processing position where the rinse liquid ejected from the rinse liquid nozzle 35 is supplied to the upper surface of the substrate W and a standby position where the rinse liquid nozzle 35 is located around the processing cup 21 in a plan view.
The pre-drying treatment liquid nozzle 39 is connected to a pre-drying treatment liquid pipe 40 for guiding the treatment liquid to the pre-drying treatment liquid nozzle 39. When the pre-drying treatment liquid valve 41 attached to the pre-drying treatment liquid pipe 40 is opened, the pre-drying treatment liquid is continuously discharged downward from the discharge port of the pre-drying treatment liquid nozzle 39. Similarly, the replacement liquid nozzle 43 is connected to a replacement liquid pipe 44 for guiding the replacement liquid to the replacement liquid nozzle 43. When the replacement liquid valve 45 attached to the replacement liquid pipe 44 is opened, the replacement liquid is continuously discharged downward from the discharge port of the replacement liquid nozzle 43.
The pretreatment liquid before drying is a solution containing a sublimate corresponding to a solute and a solvent miscible with the sublimate. The sublimating substance may be a substance that changes from a solid to a gas without being a liquid at normal temperature (the same meaning as room temperature) or normal pressure (the pressure in the substrate processing apparatus 1. For example, a value of 1 atm or the vicinity thereof). The solvent may be such a substance or may be other than the same. That is, the pretreatment liquid before drying may contain two or more substances which change from solid to gas at normal temperature or normal pressure without passing through liquid.
The sublimable substance may be any of, for example, 2-methyl-2-propanol (also referred to as t-butanol, t-butyl alcohol), alcohols such as cyclohexanol, fluorohydrocarbon compounds, 1,3, 5-trioxane (also referred to as trioxane), camphor (also referred to as camphene), naphthalene, iodine, and cyclohexane, or may be other substances.
The solvent may be at least one selected from the group consisting of pure water, IPA, HFE (hydrofluoroether), acetone, PGMEA (propylene glycol monomethyl ether acetate), PGEE (propylene glycol monoethyl ether, 1-ethoxy-2-propanol), ethylene glycol, and hydrofluorocarbons (hydrofluorocarbons), for example.
Hereinafter, an example will be described in which the sublimating substance is camphor and the solvent is any one of IPA, acetone, and PGEE. The vapor pressure of IPA is higher than the vapor pressure of camphor. Likewise, the vapor pressure of acetone and PGEE is higher than that of camphor. The vapor pressure of acetone is higher than that of IPA, which is higher than that of PGEE. The freezing point of camphor (the freezing point at 1 atm. The same applies below) is 175-177 ℃. When the solvent is any of IPA, acetone and PGEE, the solidifying point of camphor is higher than the boiling point of the solvent. The solidifying point of camphor is higher than that of the treating liquid before drying. The solidification point of the treatment liquid before drying was lower than room temperature (a value at or near 23 ℃). The substrate processing apparatus 1 is disposed in a clean room maintained at room temperature. Therefore, the pre-drying treatment liquid can be maintained as a liquid without heating the pre-drying treatment liquid. The solidification point of the pretreatment liquid before drying may be not less than room temperature.
As described later, the replacement liquid is supplied to the upper surface of the substrate W covered with the liquid film of the rinse liquid, and the pre-drying treatment liquid is supplied to the upper surface of the substrate W covered with the liquid film of the replacement liquid. The substitution liquid is a liquid which is compatible with both the rinse liquid and the pretreatment liquid before drying. The displacing liquid is, for example, IPA or HFE. The substitution liquid may be a mixed liquid of IPA and HFE, or may contain at least one of IPA and HFE and components other than these. IPA and HFE are liquids that are miscible with both water and fluorocarbon compounds.
When the replacement liquid is supplied to the upper surface of the substrate W covered with the liquid film of the rinse liquid, most of the rinse liquid on the substrate W is washed away by the replacement liquid and discharged from the substrate W. The remaining trace amount of the rinse solution is dissolved in the substitution solution and diffused in the substitution solution. The diffused rinse liquid is discharged from the substrate W together with the displacement liquid. Therefore, the rinse liquid on the substrate W can be replaced with the replacement liquid effectively. For the same reason, the replacement liquid on the substrate W can be replaced with the pretreatment liquid before drying effectively. This can reduce the rinse liquid contained in the pretreatment liquid before drying on the substrate W.
The pre-drying treatment liquid nozzle 39 is connected to a nozzle moving means 42 that moves the pre-drying treatment liquid nozzle 39 in at least one of the vertical direction and the horizontal direction. The nozzle moving means 42 horizontally moves the pre-drying treatment liquid nozzle 39 between a treatment position at which the pre-drying treatment liquid discharged from the pre-drying treatment liquid nozzle 39 is supplied to the upper surface of the substrate W and a standby position at which the pre-drying treatment liquid nozzle 39 is positioned around the treatment cup 21 in a plan view.
Similarly, the replacement liquid nozzle 43 is connected to a nozzle moving means 46 for moving the replacement liquid nozzle 43 in at least one of the vertical direction and the horizontal direction. The nozzle moving unit 46 horizontally moves the replacement liquid nozzle 43 between a processing position at which the replacement liquid ejected from the replacement liquid nozzle 43 is supplied to the upper surface of the substrate W, and a standby position at which the replacement liquid nozzle 43 is positioned around the processing cup 21 in a plan view.
The processing unit 2 includes a blocking member 51 disposed above the spin chuck 10. Fig. 2 shows an example of a disc-shaped blocking plate as the blocking member 51. The blocking member 51 includes a circular plate portion 52 horizontally disposed above the spin chuck 10. The blocking member 51 is horizontally supported by a cylindrical support shaft 53 extending upward from the center of the disk 52. The center line of the disk portion 52 is disposed on the rotation axis A1 of the substrate W. The lower surface of the circular plate portion 52 corresponds to the lower surface 51L of the blocking member 51. The lower surface 51L of the blocking member 51 is an opposing surface opposing the upper surface of the substrate W. The lower surface 51L of the blocking member 51 is parallel to the upper surface of the substrate W, and has an outer diameter equal to or larger than the diameter of the substrate W.
The blocking member 51 is connected to a blocking member lifting unit 54 that lifts the blocking member 51 vertically. The blocking member lifting unit 54 positions the blocking member 51 at an arbitrary position from an upper position (position shown in fig. 2) to a lower position. The lower position is a position where the lower surface 51L of the blocking member 51 approaches the upper surface of the substrate W to a height where the scanning nozzle such as the chemical nozzle 31 cannot enter between the substrate W and the blocking member 51. The upper position is a distant position where the blocking member 51 is retracted to a height where the scanning nozzle can enter between the blocking member 51 and the substrate W.
The plurality of nozzles include a center nozzle 55 that discharges a processing fluid such as a processing liquid or a processing gas downward through an upper center opening 61 that opens at a center of the lower surface 51L of the blocking member 51. The center nozzle 55 extends in the up-down direction along the rotation axis A1. The center nozzle 55 is disposed in a through hole penetrating the center portion of the blocking member 51 in the vertical direction. The inner peripheral surface of the blocking member 51 surrounds the outer peripheral surface of the center nozzle 55 with a gap therebetween in the radial direction (the direction orthogonal to the rotation axis A1). The center nozzle 55 is lifted and lowered together with the blocking member 51. The discharge port of the center nozzle 55 for discharging the treatment liquid is disposed above the upper center opening 61 of the blocking member 51.
The center nozzle 55 is connected to an upper gas pipe 56 for guiding the inert gas to the center nozzle 55. The substrate processing apparatus 1 may be provided with an upper temperature regulator 59 for heating or cooling the inert gas ejected from the center nozzle 55. When the upper gas valve 57 attached to the upper gas pipe 56 is opened, the inert gas is continuously discharged downward from the discharge port of the central nozzle 55 at a flow rate corresponding to the opening of the flow rate adjustment valve 58 for changing the flow rate of the inert gas. The inert gas ejected from the center nozzle 55 is nitrogen gas. The inert gas may be a gas other than nitrogen, such as helium or argon.
The inner peripheral surface of the blocking member 51 and the outer peripheral surface of the center nozzle 55 form a cylindrical upper gas flow path 62 extending vertically. The upper gas flow path 62 is connected to an upper gas pipe 63 that guides the inert gas to the upper central opening 61 of the blocking member 51. The substrate processing apparatus 1 may be provided with an upper temperature regulator 66 that heats or cools the inert gas ejected from the upper central opening 61 of the blocking member 51. When the upper gas valve 64 attached to the upper gas pipe 63 is opened, the inert gas is continuously discharged downward from the upper central opening 61 of the blocking member 51 at a flow rate corresponding to the opening of the flow rate adjusting valve 65 that changes the flow rate of the inert gas. The inert gas ejected from the upper central opening 61 of the blocking member 51 is nitrogen gas. The inert gas may be a gas other than nitrogen, such as helium or argon.
The plurality of nozzles include a lower surface nozzle 71 that ejects the processing liquid toward a central portion of the lower surface of the substrate W. The lower surface nozzle 71 includes: a nozzle disk portion disposed between the upper surface 12u of the spin base 12 and the lower surface of the substrate W; and a nozzle cylindrical portion extending downward from the nozzle disk portion. The ejection port of the lower surface nozzle 71 opens at the upper surface center portion of the nozzle disk portion. When the substrate W is held by the spin chuck 10, the ejection port of the lower surface nozzle 71 faces the central portion of the lower surface of the substrate W in the vertical direction.
The lower surface nozzle 71 is connected to a heating fluid pipe 72 for guiding hot water (pure water having a temperature higher than room temperature) as an example of the heating fluid to the lower surface nozzle 71. The pure water supplied to the lower surface nozzle 71 is heated by a lower heater 75 attached to the heating fluid pipe 72. When the heating fluid valve 73 attached to the heating fluid pipe 72 is opened, the hot water is continuously discharged upward from the discharge port of the lower nozzle 71 at a flow rate corresponding to the opening degree of the flow rate adjusting valve 74 that changes the flow rate of the hot water. Thereby, hot water is supplied to the lower surface of the substrate W.
The lower surface nozzle 71 is also connected to a cooling fluid pipe 76 for guiding cold water (pure water having a temperature lower than room temperature) as an example of the cooling fluid to the lower surface nozzle 71. The pure water supplied to the lower surface nozzle 71 is cooled by a cooler 79 attached to the cooling fluid pipe 76. When the cooling fluid valve 77 attached to the cooling fluid pipe 76 is opened, the cold water is continuously discharged upward from the discharge port of the lower nozzle 71 at a flow rate corresponding to the opening degree of the flow rate regulating valve 78 that changes the flow rate of the cold water. Thereby, cold water is supplied to the lower surface of the substrate W.
The outer peripheral surface of the lower nozzle 71 and the inner peripheral surface of the spin base 12 form a cylindrical lower gas flow path 82 extending vertically. The lower gas flow path 82 includes a lower central opening 81 that opens at a central portion of the upper surface 12u of the spin base 12. The lower gas flow path 82 is connected to a lower gas pipe 83 that guides the inert gas to the lower central opening 81 of the spin base 12. The substrate processing apparatus 1 may be provided with a lower temperature regulator 86 for heating or cooling the inert gas discharged from the lower central opening 81 of the spin base 12. When the lower gas valve 84 attached to the lower gas pipe 83 is opened, the inert gas is continuously discharged upward from the lower central opening 81 of the swivel base 12 at a flow rate corresponding to the opening of the flow rate adjustment valve 85 that changes the flow rate of the inert gas.
The inert gas ejected from the lower central opening 81 of the spin base 12 is nitrogen gas. The inert gas may be a gas other than nitrogen, such as helium or argon. When nitrogen gas is ejected from the lower central opening 81 of the spin base 12 while the substrate W is held by the spin chuck 10, the nitrogen gas flows radially in all directions between the lower surface of the substrate W and the upper surface 12u of the spin base 12. Thereby, the space between the substrate W and the spin base 12 is filled with nitrogen gas.
Next, a pretreatment liquid supply unit before drying will be described.
Fig. 3 is a schematic view showing a pretreatment-drying treatment liquid supply unit provided in the substrate processing apparatus 1.
The substrate processing apparatus 1 includes a pretreatment-drying-liquid supply unit that supplies a pretreatment-liquid to the pretreatment-liquid nozzle 39 via a pretreatment-liquid pipe 40.
The pretreatment liquid supply unit includes: a 1 st tank 87A for storing a pretreatment liquid before drying; a 1 st circulation pipe 88A for circulating the pre-drying treatment liquid in the 1 st tank 87A; a 1 st pump 89A for feeding the pre-drying treatment liquid in the 1 st tank 87A to the 1 st circulation pipe 88A; and a 1 st individual pipe 90A for guiding the pre-drying treatment liquid in the 1 st circulation pipe 88A to the pre-drying treatment liquid pipe 40. The pretreatment liquid supply unit further comprises: a 1 st on-off valve 91A for opening and closing the inside of the 1 st individual pipe 90A; and a 1 st flow rate adjustment valve 92A for changing the flow rate of the pre-drying treatment liquid supplied from the 1 st individual pipe 90A to the pre-drying treatment liquid pipe 40.
The pretreatment liquid supply unit includes: a 2 nd tank 87B for storing a drying pretreatment liquid; a 2 nd circulation pipe 88B for circulating the pre-drying treatment liquid in the 2 nd tank 87B; a 2 nd pump 89B for feeding the pre-drying treatment liquid in the 2 nd tank 87B to the 2 nd circulation pipe 88B; and a 2 nd individual pipe 90B for guiding the pre-drying treatment liquid in the 2 nd circulation pipe 88B to the pre-drying treatment liquid pipe 40. The pretreatment liquid supply unit further comprises: a 2 nd opening/closing valve 91B for opening/closing the inside of the 2 nd individual pipe 90B; a 2 nd flow rate adjustment valve 92B for changing the flow rate of the pre-drying treatment liquid supplied from the 2 nd individual pipe 90B to the pre-drying treatment liquid pipe 40.
The concentration of the pre-drying treatment liquid in the 1 st tank 87A (the concentration of the sublimating substance contained in the pre-drying treatment liquid) is different from the concentration of the pre-drying treatment liquid in the 2 nd tank 87B. Accordingly, when the 1 st on-off valve 91A and the 2 nd on-off valve 91B are opened, the drying pretreatment liquids having different concentrations are mixed in the drying pretreatment liquid piping 40, and the uniformly mixed drying pretreatment liquid is discharged from the drying pretreatment liquid nozzle 39. When the opening degree of at least one of the 1 st flow rate adjustment valve 92A and the 2 nd flow rate adjustment valve 92B is changed, the concentration of the pre-drying treatment liquid discharged from the pre-drying treatment liquid nozzle 39 is changed.
The control device 3 sets the opening degrees of the 1 st on-off valve 91A, the 2 nd on-off valve 91B, the 1 st flow rate regulating valve 92A, and the 2 nd flow rate regulating valve 92B based on the concentration of the pre-drying treatment liquid specified in the process described later. For example, when the concentration of the pre-drying treatment liquid specified in the process matches the concentration of the pre-drying treatment liquid in the 1 st tank 87A, the 1 st on-off valve 91A is opened, and the 2 nd on-off valve 91B is closed. When the concentration of the pre-drying treatment liquid specified in the process is a value between the concentration of the pre-drying treatment liquid in the 1 st tank 87A and the concentration of the pre-drying treatment liquid in the 2 nd tank 87B, both the 1 st on-off valve 91A and the 2 nd on-off valve 91B are opened, and the opening degrees of the 1 st flow rate regulating valve 92A and the 2 nd flow rate regulating valve 92B are adjusted. Thus, the concentration of the pre-drying treatment liquid discharged from the pre-drying treatment liquid nozzle 39 is close to the concentration of the pre-drying treatment liquid designated in the process.
Fig. 4 is a block diagram showing hardware of the control device 3.
The control device 3 is a computer including a computer main body 3a and a peripheral device 3b connected to the computer main body 3 a. The computer main body 3a includes: a CPU93 (central processing unit: central processing unit) for executing various commands; and a main storage 94 storing information. The peripheral device 3b includes: an auxiliary storage device 95 for storing information such as the program P; a reading device 96 that reads information from the removable medium M; and a communication device 97 for communicating with other devices such as a host computer.
The control device 3 is connected to an input device 98 and a display device 99. The input device 98 is operated when an operator such as a user or a maintenance person inputs information into the substrate processing apparatus 1. The information is displayed on the screen of the display device 99. The input device 98 may be any of a keyboard, a pointing device, and a touch panel, or may be other devices. A touch panel display having both the input device 98 and the display device 99 may be provided in the substrate processing apparatus 1.
The CPU93 executes the program P stored in the auxiliary storage 95. The program P in the auxiliary storage device 95 may be installed in the control device 3 in advance, may be transferred from the removable medium M to the auxiliary storage device 95 via the reading device 96, and may be transferred from an external device such as a host computer to the auxiliary storage device 95 via the communication device 97.
The auxiliary storage device 95 and the removable medium M are nonvolatile memories that maintain storage even when power is not supplied. The auxiliary storage device 95 is a magnetic storage device such as a hard disk drive. The removable medium M is a semiconductor memory such as an optical disc such as a CD or a memory card. The removable medium M is an example of a computer-readable recording medium on which the program P is recorded. The removable medium M is a non-transitory tangible recording medium.
The auxiliary storage 95 stores a plurality of processes. The process is information defining the processing contents, processing conditions, and processing steps of the substrate W. The plurality of processes are different from each other in at least one of the processing contents, the processing conditions, and the processing steps of the substrate W. The control device 3 controls the substrate processing device 1 in such a manner that the substrate W is processed in accordance with a process specified by the host computer. The following steps are performed by controlling the substrate processing apparatus 1 by the control apparatus 3. In other words, the control device 3 is programmed to execute the following steps.
Next, an example of the process of the substrate W according to embodiment 1 will be described.
The processed substrate W is a semiconductor wafer such as a silicon wafer. The surface of the substrate W corresponds to a device formation surface for forming devices such as transistors and capacitors. The substrate W may be a substrate W having a pattern P1 (see fig. 6A) formed on a surface of the substrate W serving as a pattern formation surface, or may be a substrate W having no pattern P1 formed on a surface of the substrate W. In the latter case, the pattern P1 may be formed in a chemical supply step described later.
Fig. 5 is a process diagram for explaining an example of processing of the substrate W according to embodiment 1. Fig. 6A to 6C are schematic views showing a state of the substrate W when the process of the substrate W shown in fig. 5 is performed.
Hereinafter, reference is made to fig. 2 and 5. Reference is made to fig. 6A to 6C as appropriate.
The carry-in step (step S1 of fig. 5) is performed to carry in the substrate W into the chamber 4 when the substrate processing apparatus 1 is used to process the substrate W.
Specifically, the center robot CR (see fig. 1) supports the substrate W with the hand H1 while allowing the hand H1 to enter the chamber 4 in a state where the blocking member 51 is located at the upper position, all the shields 24 are located at the lower position, and all the scanning nozzles are located at the standby position. Then, the center robot CR places the substrate W on the hand H1 on the plurality of chuck pins 11 in a state where the surface of the substrate W is upward. Then, the chuck pins 11 are pressed against the outer peripheral surface of the substrate W to hold the substrate W. The center robot CR withdraws the hand H1 from the inside of the chamber 4 after placing the substrate W on the spin chuck 10.
Next, the upper gas valve 64 and the lower gas valve 84 are opened, and the nitrogen gas starts to be discharged from the upper central opening 61 of the blocking member 51 and the lower central opening 81 of the spin base 12. Thereby, the space between the substrate W and the blocking member 51 is filled with nitrogen gas. Likewise, the space between the substrate W and the spin base 12 is filled with nitrogen gas. On the other hand, the shield elevating unit 27 elevates at least one shield 24 from the lower position to the upper position. Then, the rotation motor 14 is driven to start rotation of the substrate W (step S2 in fig. 5). Thereby, the substrate W rotates at the liquid supply speed.
Next, a chemical liquid supplying step (step S3 in fig. 5) of supplying a chemical liquid to the upper surface of the substrate W to form a chemical liquid film covering the entire upper surface of the substrate W is performed.
Specifically, the nozzle moving unit 34 moves the chemical nozzle 31 from the standby position to the processing position in a state where the blocking member 51 is located at the upper position and the at least one shield 24 is located at the upper position. Then, the chemical liquid valve 33 is opened, and the chemical liquid nozzle 31 starts to discharge the chemical liquid. When a predetermined time has elapsed since the opening of the chemical solution valve 33, the chemical solution valve 33 is closed, and the discharge of the chemical solution is stopped. Then, the nozzle moving unit 34 moves the chemical nozzle 31 to the standby position.
The chemical liquid ejected from the chemical liquid nozzle 31 collides with the upper surface of the substrate W rotating at the liquid supply speed, and then flows outward along the upper surface of the substrate W by centrifugal force. Therefore, the chemical solution is supplied to the entire upper surface of the substrate W, and a liquid film of the chemical solution is formed to cover the entire upper surface of the substrate W. When the chemical solution is discharged from the chemical solution nozzle 31, the nozzle moving unit 34 may move the landing position so that the chemical solution passes through the central portion and the outer peripheral portion with respect to the landing position on the upper surface of the substrate W, or may rest the landing position at the central portion.
Next, a rinse liquid supply step (step S4 in fig. 5) is performed in which pure water as an example of a rinse liquid is supplied to the upper surface of the substrate W, thereby washing away the chemical liquid on the substrate W.
Specifically, the nozzle moving unit 38 moves the rinse liquid nozzle 35 from the standby position to the treatment position in a state where the blocking member 51 is located at the upper position and the at least one shield 24 is located at the upper position. Then, the rinse liquid valve 37 is opened, and the rinse liquid nozzle 35 starts to discharge the rinse liquid. Before starting the ejection of the pure water, the shield elevating unit 27 may vertically move at least one shield 24 in order to switch the shield 24 blocking the liquid discharged from the substrate W. When a predetermined time has elapsed since the opening of the rinse liquid valve 37, the rinse liquid valve 37 is closed, and the discharge of the rinse liquid is stopped. Then, the nozzle moving unit 38 moves the rinse liquid nozzle 35 to the standby position.
The pure water discharged from the rinse liquid nozzle 35 collides with the upper surface of the substrate W rotated at the liquid supply speed, and then flows outward along the upper surface of the substrate W by centrifugal force. The chemical solution on the substrate W is replaced with pure water ejected from the rinse solution nozzle 35. Thereby, a liquid film of pure water is formed which covers the entire upper surface of the substrate W. When the rinse liquid nozzle 35 ejects the deionized water, the nozzle moving means 38 may move the deionized water so as to pass through the center portion and the outer peripheral portion with respect to the deionized water on the upper surface of the substrate W, or may rest the deionized water on the center portion.
Next, a replacement liquid supply step (step S5 in fig. 5) is performed in which a replacement liquid that is compatible with both the rinse liquid and the pretreatment liquid before drying is supplied to the upper surface of the substrate W, and the pure water on the substrate W is replaced with the replacement liquid.
Specifically, the nozzle moving unit 46 moves the replacement liquid nozzle 43 from the standby position to the processing position in a state where the blocking member 51 is located at the upper position and the at least one shield 24 is located at the upper position. Then, the replacement liquid valve 45 is opened, and the replacement liquid nozzle 43 starts to discharge the replacement liquid. Before starting ejection of the replacement liquid, the shield elevating unit 27 may vertically move at least one shield 24 in order to switch the shield 24 blocking the liquid discharged from the substrate W. When a predetermined time has elapsed since the replacement liquid valve 45 was opened, the replacement liquid valve 45 is closed, and the ejection of the replacement liquid is stopped. Then, the nozzle moving unit 46 moves the replacement liquid nozzle 43 to the standby position.
After the replacement liquid ejected from the replacement liquid nozzle 43 collides with the upper surface of the substrate W rotating at the liquid supply speed, the replacement liquid flows outward along the upper surface of the substrate W by centrifugal force. The pure water on the substrate W is replaced with the replacement liquid ejected from the replacement liquid nozzle 43. Thereby, a liquid film of the replacement liquid covering the entire upper surface of the substrate W is formed. When the replacement liquid nozzle 43 discharges the replacement liquid, the nozzle moving unit 46 may move the landing position so that the landing position of the replacement liquid on the upper surface of the substrate W passes through the center portion and the outer peripheral portion, or may rest the landing position at the center portion. After forming the liquid film of the replacement liquid covering the entire upper surface of the substrate W, the replacement liquid nozzle 43 may be stopped from ejecting the replacement liquid, and the substrate W may be rotated at a speed of immersion (pump) (for example, a speed exceeding 0 and 20rpm or less).
Next, a pre-drying treatment liquid supply step (step S6 in fig. 5) is performed to supply a pre-drying treatment liquid to the upper surface of the substrate W, thereby forming a liquid film of the pre-drying treatment liquid on the substrate W.
Specifically, the nozzle moving unit 42 moves the pre-drying treatment liquid nozzle 39 from the standby position to the treatment position in a state where the blocking member 51 is located at the upper position and the at least one shield 24 is located at the upper position. Then, the pre-drying treatment liquid valve 41 is opened, and the pre-drying treatment liquid nozzle 39 starts to discharge the pre-drying treatment liquid. Before starting to eject the pre-drying treatment liquid, the shield elevating unit 27 may vertically move at least one shield 24 in order to switch the shield 24 blocking the liquid discharged from the substrate W. When a predetermined time has elapsed since the opening of the pre-drying treatment liquid valve 41, the pre-drying treatment liquid valve 41 is closed, and the discharge of the pre-drying treatment liquid is stopped. Then, the nozzle moving unit 42 moves the pre-drying treatment liquid nozzle 39 to the standby position.
After the pre-drying treatment liquid ejected from the pre-drying treatment liquid nozzle 39 collides with the upper surface of the substrate W rotated at the liquid supply speed, the pre-drying treatment liquid flows outward along the upper surface of the substrate W due to centrifugal force. The replacement liquid on the substrate W is replaced with the pre-drying treatment liquid discharged from the pre-drying treatment liquid nozzle 39. Thereby, a liquid film of the drying pretreatment liquid covering the entire upper surface of the substrate W is formed. When the pre-drying treatment liquid nozzle 39 discharges the pre-drying treatment liquid, the nozzle moving means 42 may move the landing position so that the landing position of the pre-drying treatment liquid on the upper surface of the substrate W passes through the central portion and the outer peripheral portion, or may rest the landing position at the central portion.
Next, a film thickness reduction step (step S7 in fig. 5) is performed in which a part of the pre-drying treatment liquid on the substrate W is removed, and the film thickness (thickness of the liquid film) of the pre-drying treatment liquid on the substrate W is reduced while maintaining a state in which the entire upper surface of the substrate W is covered with the liquid film of the pre-drying treatment liquid.
Specifically, the rotation motor 14 maintains the rotation speed of the substrate W at the film thickness reduction speed in a state where the blocking member 51 is located at the lower position. The film thickness reduction speed may be the same as or different from the liquid supply speed. The pre-drying treatment liquid on the substrate W is discharged outward from the substrate W by centrifugal force even after stopping the discharge of the pre-drying treatment liquid. Therefore, the thickness of the liquid film of the pre-drying treatment liquid on the substrate W is reduced. After the pre-drying treatment liquid on the substrate W is discharged to some extent, the discharge amount of the pre-drying treatment liquid from the substrate W per unit time is reduced to zero or close to zero. Thereby, the thickness of the liquid film of the pre-drying treatment liquid on the substrate W is stabilized at a value corresponding to the rotation speed of the substrate W.
Next, a solidification forming process (step S8 of fig. 5) is performed, that is, the pretreatment liquid before drying on the substrate W is solidified, thereby forming a solidified body 101 containing a sublimating substance on the substrate W (see fig. 6B).
Specifically, in a state where the blocking member 51 is located at the lower position, the rotation motor 14 maintains the rotation speed of the substrate W at the solidification forming speed. The solidification forming speed may be the same as or different from the liquid supplying speed. Further, the upper gas valve 57 is opened, and the nitrogen gas starts to be discharged from the center nozzle 55. The opening degree of the flow rate adjustment valve 65 may be changed in addition to or instead of opening the upper gas valve 57, so that the flow rate of the nitrogen gas discharged from the upper central opening 61 of the blocking member 51 may be increased.
When the rotation of the substrate W is started at the solidification speed, the evaporation of the pre-drying treatment liquid is promoted, and a part of the pre-drying treatment liquid on the substrate W is evaporated. Since the vapor pressure of the solvent is higher than the vapor pressure of the sublimating substance corresponding to the solute, the solvent evaporates at a higher evaporation rate than the evaporation rate of the sublimating substance. Therefore, the concentration of the sublimating substance gradually increases, and the film thickness of the treatment liquid before drying gradually decreases. The freezing point of the treatment liquid before drying increases with an increase in the concentration of the sublimating substance. As can be seen from a comparison of fig. 6A and 6B, when the solidification point of the pre-drying treatment liquid reaches the temperature of the pre-drying treatment liquid, the pre-drying treatment liquid starts to solidify, and a solidified body 101 corresponding to a solidified film covering the entire upper surface of the substrate W is formed.
Next, a sublimation process (step S9 of fig. 5) is performed to sublimate the solidified material 101 on the substrate W, thereby removing the solidified material 101 from the upper surface of the substrate W.
Specifically, the rotation motor 14 maintains the rotation speed of the substrate W at the sublimation speed in a state where the blocking member 51 is located at the lower position. The sublimation rate may be the same as or different from the liquid supply rate. When the upper gas valve 57 is closed, the upper gas valve 57 is opened, and the nitrogen gas is started to be discharged from the center nozzle 55. The opening degree of the flow rate adjustment valve 65 may be changed in addition to or instead of opening the upper gas valve 57, so that the flow rate of the nitrogen gas discharged from the upper central opening 61 of the blocking member 51 may be increased. When a predetermined time has elapsed since the start of rotation of the substrate W at the sublimation rate, the rotation motor 14 is stopped to stop the rotation of the substrate W (step S10 in fig. 5).
When the rotation of the substrate W is started at a sublimation rate, the solidified material 101 on the substrate W starts to sublimate, and a gas containing a sublimating substance is generated from the solidified material 101 on the substrate W. The gas (gas containing a sublimate) generated from the solid 101 flows radially in the space between the substrate W and the blocking member 51, and is discharged from above the substrate W. Further, when a certain amount of time has elapsed from the start of sublimation, as shown in fig. 6C, all of the solidified material 101 is removed from the substrate W.
Next, a carry-out process of carrying out the substrate W from the chamber 4 is performed (step S11 in fig. 5).
Specifically, the blocking member lifting unit 54 lifts the blocking member 51 to the upper position, and the shield lifting unit 27 lowers all of the shields 24 to the lower position. Further, the upper gas valve 64 and the lower gas valve 84 are closed, and the nitrogen gas discharge is stopped by the upper central opening 61 of the blocking member 51 and the lower central opening 81 of the spin base 12. Then, the center robot CR brings the hand H1 into the chamber 4. After the chuck pins 11 release the grip of the substrate W, the center robot CR supports the substrate W on the spin chuck 10 by the hand H1. Then, the center robot CR supports the substrate W with the hand H1 and withdraws the hand H1 from the chamber 4. Thereby, the processed substrate W is carried out of the chamber 4.
Fig. 7 is a view showing an example of an image in which the thickness of the liquid film of the pre-drying treatment liquid on the substrate W is reduced by evaporation of the solvent.
In fig. 7, the thickness of the liquid film when the initial concentration of the sublimating substance is the reference concentration is shown by a solid line, the thickness of the liquid film when the initial concentration of the sublimating substance is the low concentration is shown by a one-dot chain line, and the thickness of the liquid film when the initial concentration of the sublimating substance is the high concentration is shown by a two-dot chain line. The reference concentration is a concentration higher than the low concentration and lower than the high concentration. The initial concentration of the sublimating substance is the concentration of the sublimating substance in the pre-drying treatment liquid before being supplied to the substrates W.
If the concentration of the sublimating substance in the pretreatment liquid before drying is the same, the thickness T1 (see fig. 6B) of the solidified material 101 formed on the substrate W depends on the film thickness (thickness of the liquid film) of the pretreatment liquid before forming the solidified material 101. That is, when the film thickness of the pre-drying treatment liquid is large, a thick solidified body 101 is formed, and when the film thickness of the pre-drying treatment liquid is small, a thin solidified body 101 is formed. Therefore, by changing the film thickness of the treatment liquid before drying, the thickness T1 of the solidified material 101 can be changed.
When the rotation speed of the substrate W is increased, the pre-drying treatment liquid is discharged from the substrate W by centrifugal force, and the film thickness of the pre-drying treatment liquid on the substrate W is reduced. At this time, when the gas is ejected toward the upper surface of the substrate W, the pressure of the gas is applied to the pre-drying treatment liquid, and the film thickness of the pre-drying treatment liquid on the substrate W is further reduced. However, when the film thickness is reduced to a certain extent, the flow velocity in the liquid film extremely decreases, and therefore, even if the rotation speed or the flow rate of the gas is increased, the film thickness does not change greatly. Conversely, when the rotational speed and the flow rate of the gas become excessively high, the upper surface of the substrate W is partially exposed from the liquid film.
Therefore, even if the rotation speed of the substrate W and the flow rate of the gas are changed, the film thickness of the pre-drying treatment liquid before forming the solidified body 101 cannot be made extremely thin, and the extremely thin solidified body 101 cannot be formed. Therefore, when forming an extremely thin solidified body 101 (e.g., a solidified body 101 having a thickness of more than 0 and 1 μm or less) covering the entire upper surface of the substrate W, or changing the thickness T1 of the solidified body 101 within an extremely thin range (e.g., a range of more than 0 and 1 μm or less), it is necessary to change the initial concentration of the sublimating substance.
In fig. 7, the film thickness of the treatment liquid before drying before evaporating the solvent is constant regardless of the initial concentration of the sublimating substance. As shown in fig. 7, when the temperature of the treatment liquid before drying is the same, the concentration of the sublimate at the start of precipitation of the solidified material 101 is constant regardless of the initial concentration of the sublimate. When the solvent is evaporated to form the solidified body 101, the concentration of the sublimate gradually increases, and the film thickness of the treatment liquid before drying gradually decreases. The freezing point of the treatment liquid before drying increases with an increase in the concentration of the sublimating substance. When the solidification point of the drying pretreatment liquid reaches the temperature of the drying pretreatment liquid, the drying pretreatment liquid starts to solidify, and a solidified body 101 is formed on the substrate W.
As shown in fig. 7, when the initial concentration of the sublimating substance is the reference concentration, a solidified material 101 having a reference thickness Tr is formed. When the initial concentration of the sublimating substance is low, the amount of the sublimating substance contained in the treatment liquid before drying is small, and therefore, the solidified body 101 thinner than the reference thickness Tr is formed. When the initial concentration of the sublimating substance is high, the amount of the sublimating substance contained in the treatment liquid before drying is large, and therefore, the solidified body 101 thicker than the reference thickness Tr is formed. Therefore, by controlling the initial concentration of the sublimating substance, the thickness T1 of the solidified material 101 can be changed within an extremely thin range.
Fig. 8 is a graph showing an example of the relationship between the initial concentration of the sublimating substance and the thickness T1 of the solidified material 101. Vol% in fig. 8 represents the volume percentage concentration. When the pretreatment liquid before drying changes to the solidified body 101, the color of the substance on the substrate W changes from transparent to non-transparent. When the film thickness of the transparent pre-drying treatment liquid is measured by the spectroscopic interferometry, the measured value changes when the non-transparent solidified material 101 is formed. The value immediately before this change occurs is shown in fig. 8 as the thickness T1 of the solidified body 101.
In FIG. 8, when the initial concentration of the sublimate is 0.5vol%, the thickness T1 of the solidified body 101 is about 100. Mu.m, and when the initial concentration of the sublimate is 1.23vol%, the thickness T1 of the solidified body 101 is about 200. Mu.m. The initial concentration of the sublimating substance is substantially in a proportional relationship with the thickness T1 of the solidification body 101, and when the initial concentration of the sublimating substance increases, the thickness T1 of the solidification body 101 increases by a certain proportion. Therefore, by changing the initial concentration of the sublimating substance, the thickness T1 of the solidified material 101 can be changed within an extremely thin range.
Fig. 9 is a table showing an example of the embedding rate and the collapse rate of the pattern P1 obtained when a plurality of samples on which the pattern P1 having the same shape and strength is formed are treated while changing the initial concentration of camphor. Fig. 10 is a line graph showing a relationship between the concentration of camphor and the collapse rate of the pattern P1 in fig. 9.
Fig. 9 and 10 show the collapse rate of the pattern P1 when the sublimable substance is camphor and the solvent is IPA. The conditions other than the initial concentration of camphor were the same in the measurement conditions 1-1 to 1-13 shown in FIGS. 9 and 10. Wt% in FIG. 9 represents the mass percent concentration. This is also the same as in the other figures of fig. 14 and the like.
The collapse rate of the pattern P1 is a value obtained by multiplying the ratio of the number of collapsed patterns P1 to the total number of patterns P1 by one hundred. The embedding rate is a value obtained by multiplying a ratio of the thickness T1 (see fig. 6B) of the solidified body 101 to the height Hp (see fig. 6B) of the pattern P1 by one hundred. That is, the embedding rate can be obtained from a calculation formula ((thickness T1 of the solidified material 101/height Hp of the pattern P1) ×100).
As shown in measurement condition 1-1 of FIG. 9, the collapse rate of pattern P1 was 83.5% when the initial concentration of camphor was 0.52 wt%.
As shown in measurement condition 1-2 of FIG. 9, the collapse rate of pattern P1 was 83.1% at an initial concentration of 0.62% by weight of camphor.
As shown in measurement conditions 1 to 3 of FIG. 9, the collapse rate of the pattern P1 was 76.2% at an initial concentration of 0.69wt% of camphor.
As shown in measurement conditions 1 to 4 of FIG. 9, the collapse rate of the pattern P1 was 36.1% at an initial concentration of 0.78wt% of camphor.
As shown in measurement conditions 1 to 13 of FIG. 9, the collapse rate of pattern P1 was 91.0% when the initial concentration of camphor was 7.76 wt%.
As shown in the measurement conditions 1 to 12 of FIG. 9, the collapse rate of the pattern P1 was 91.7% when the initial concentration of camphor was 4.03 wt%.
As shown in the measurement conditions 1 to 11 of FIG. 9, the collapse rate of the pattern P1 was 87.0% when the initial concentration of camphor was 2.06% by weight.
As shown in the measurement conditions 1 to 10 of FIG. 9, the collapse rate of the pattern P1 was 46.8% at an initial concentration of 1.55% by weight of camphor.
As can be seen from fig. 9 and 10, when the initial concentration of camphor was increased from 0.62wt% to 0.69wt%, the collapse rate of pattern P1 was decreased (measurement condition 1-2→measurement condition 1-3). Further, when the initial concentration of camphor was increased from 0.69 to 0.78wt%, the collapse rate of the pattern P1 was drastically reduced (measurement condition 1-3. Fwdarw. Measurement condition 1-4).
On the other hand, when the initial concentration of camphor was reduced from 2.06wt% to 1.55wt%, the collapse rate of the pattern P1 was drastically reduced (measurement condition 1-11. Fwdarw. Measurement condition 1-10).
Thus, the initial concentration of camphor is preferably more than 0.62wt% and less than 2.06wt%, more preferably 0.78wt% or more and less than 2.06wt%.
When the initial concentration of camphor is in the range of more than 0.62wt% and less than 2.06wt%, the collapse rate of the pattern P1 is less than 87.0%.
When the initial concentration of camphor is in the range of 0.78wt% or more and 1.55wt% or less, the collapse rate of the pattern P1 is 46.8% or less.
When the initial concentration of camphor is in the range of 0.89wt% or more and 1.24wt% or less, the collapse rate of the pattern P1 is 17.6% or less. In terms of the collapse rate of the pattern P1, the minimum at the initial concentration of camphor of 0.89wt% is 8.32%.
Thus, the initial concentration of camphor may be 0.78wt% or more and 1.55wt% or less, and may be 0.89wt% or more and 1.24wt% or less.
Fig. 11 is a line graph showing a relationship between the embedding rate and the collapse rate of the pattern P1 in fig. 9.
As shown in measurement condition 1-1 of fig. 9, the collapse rate of the pattern P1 was 83.5% when the embedding rate was 65%.
As shown in measurement condition 1-2 of fig. 9, the collapse rate of the pattern P1 was 83.1% when the embedding rate was 76%.
As shown in measurement conditions 1 to 3 of fig. 9, the collapse rate of the pattern P1 was 76.2% when the embedding rate was 83%.
As shown in measurement conditions 1 to 4 of fig. 9, the collapse rate of the pattern P1 was 36.1% when the embedding rate was 91%.
As shown in measurement conditions 1 to 13 of fig. 9, the collapse rate of the pattern P1 was 91.0% when the embedding rate was 797%.
As shown in measurement conditions 1 to 12 of fig. 9, the collapse rate of the pattern P1 was 91.7% when the embedding rate was 418%.
As shown in measurement conditions 1 to 11 of fig. 9, the collapse rate of the pattern P1 was 87.0% when the embedding rate was 219%.
As shown in measurement conditions 1 to 10 of fig. 9, the collapse rate of the pattern P1 was 46.8% when the embedding rate was 168%.
As can be seen from fig. 9 and 11, the collapse rate of the pattern P1 decreases when the embedding rate increases from 76% to 83% (measurement condition 1-2→measurement condition 1-3). When the embedding rate was increased from 83% to 91%, the collapse rate of the pattern P1 was drastically reduced (measurement conditions 1 to 3. Fwdarw. Measurement conditions 1 to 4).
On the other hand, when the embedding rate was reduced from 219% to 168%, the collapse rate of the pattern P1 was drastically reduced (measurement conditions 1 to 11→measurement conditions 1 to 10).
Therefore, the embedding rate is preferably more than 76% and less than 219%, and more preferably 83% or more and less than 219%.
When the embedding rate is in the range of more than 76% and less than 219%, the collapse rate of the pattern P1 is less than 87.0%.
When the embedding rate is in the range of 91% to 168%, the collapse rate of the pattern P1 is 46.8% or less.
When the embedding rate is in the range of 102% to 138%, the collapse rate of the pattern P1 is 17.6% or less. When the embedding rate was 102%, the collapse rate of the pattern P1 was the lowest, and was 8.32%.
Therefore, the embedding rate may be 91% or more and 168% or less, and may be 102% or more and 138% or less.
As mentioned above, the initial concentration of camphor is preferably in excess of 0.62wt% and less than 2.06wt%. As shown in FIG. 9, the initial concentration of camphor was 0.62wt% and the intercalation rate was 76%. At an initial concentration of 2.06wt% of camphor, the intercalation rate was 219%. Therefore, in this example, if the initial concentration of camphor is set to a value within the preferable range, the insertion rate is also automatically set to a value within the preferable range.
Fig. 12A and 12B are schematic diagrams for explaining a mechanism assumed for a phenomenon in which the collapse rate of the pattern P1 increases when the solidified body 101 is excessively thick. Fig. 13A and 13B are schematic diagrams for explaining a mechanism assumed for a phenomenon in which the collapse rate of the pattern P1 increases when the solidified body 101 is excessively thin.
As shown in fig. 11, when the solidified material 101 is too thick (when the embedding rate is too high), the collapse rate of the pattern P1 increases. In addition, even if the thickness T1 of the solidified body 101 is smaller than the height Hp of the pattern P1, the collapse rate of the pattern P1 may be low, but when the solidified body 101 is too thin (when the embedding rate is too low), the collapse rate of the pattern P1 may be high. Hereinafter, the mechanism envisaged for these phenomena is explained.
First, a mechanism assumed for a phenomenon in which the collapse rate of the pattern P1 increases when the solidified body 101 is excessively thick will be described.
When the evaporation of IPA contained in the pre-drying treatment liquid proceeds, the concentration of camphor in the pre-drying treatment liquid gradually increases, and the freezing point of the pre-drying treatment liquid gradually increases. When the solidification point of the drying pretreatment liquid reaches the temperature of the drying pretreatment liquid, the drying pretreatment liquid starts to solidify, and a solidified body 101 containing camphor is formed on the substrate W.
When the embedding rate is 100% or more, that is, when the thickness T1 (see fig. 6B) of the solidified material 101 is equal to or greater than the height Hp (see fig. 6B) of the pattern P1, the pre-drying treatment liquid is present not only between the patterns P1 but also above the patterns P1 before the solidified material 101 is formed. In the substrate W such as a semiconductor wafer, the interval between the adjacent 2 convex patterns P1 is narrow, and thus the solidification point of the pre-drying treatment liquid located between the patterns P1 is lowered. Therefore, the freezing point of the drying pretreatment liquid located between the patterns P1 is lower than the freezing point of the drying pretreatment liquid located above the patterns P1.
When the solidification point of the pre-drying treatment liquid located above the patterns P1 is higher than the solidification point of the pre-drying treatment liquid located between the patterns P1, solidification of the pre-drying treatment liquid starts at a position other than between the patterns P1. Specifically, as shown in fig. 12A, nuclei of camphor are generated in the surface layer of the pre-drying treatment liquid, that is, in the liquid layer located in the range from the upper surface (liquid surface) of the pre-drying treatment liquid to the upper surface of the pattern P1, and the nuclei become gradually larger. Then, after a certain period of time, the entire surface layer of the pretreatment liquid is solidified to form a solidified body 101.
Here, when the solidification point of the pre-drying treatment liquid located between the patterns P1 is lower than the solidification point of the pre-drying treatment liquid located above the patterns P1, as shown in fig. 12B, the pre-drying treatment liquid located between the patterns P1 may remain in a liquid state without solidifying. In this case, an interface between the solid (solidified material 101) and the liquid (pre-drying treatment liquid) is formed in the vicinity of the pattern P1. Fig. 12B shows a state in which an unclear interface (unclear interface) of solid and liquid is located between the patterns P1.
The surface free energies of solids and liquids are different from each other. In the case where an unclear interface between the solid (solidified body 101) and the liquid (pre-drying treatment liquid) is located between the patterns P1, a force due to the laplace pressure is applied to the patterns P1. At this time, the force applied to the pattern P1 increases as the solidified body 101 becomes thicker. Therefore, when the solidified body 101 is too thick, the collapse force for collapsing the pattern P1 exceeds the strength of the pattern P1, and the collapse rate of the pattern P1 increases. It is considered that the collapse rate of the pattern P1 increases due to such a mechanism.
Next, a mechanism assumed for the phenomenon that the collapse rate of the pattern P1 is also reduced when the embedding rate is less than 100% will be described.
When the solidified body 101 is formed, the upper surface (liquid surface) of the pre-drying treatment liquid gradually approaches the lower end of the pattern P1 as the evaporation of the IPA proceeds. When the thickness T1 of the solidified material 101 is significantly smaller than the height Hp of the pattern P1, as shown in fig. 13A, the upper surface of the pre-drying treatment liquid moves between 2 adjacent convex patterns P1 before the entire pre-drying treatment liquid solidifies. That is, the interface between the gas and the liquid (pre-drying treatment liquid) moves between the patterns P1. Therefore, it is considered that a force due to the surface tension of the treatment liquid before drying is applied to the pattern P1, and the pattern P1 collapses. Further, as shown in fig. 13B, it is considered that the solidified body 101 is formed in a state where the pattern P1 is collapsed.
It is considered that, when the thickness T1 of the solidified material 101 is slightly smaller than the height Hp of the pattern P1, the interface between the gas and the liquid moves between the patterns P1. However, it is considered that in this case, nuclei of camphor have been formed between the patterns P1, and the nuclei become large to some extent. In this case, the inclination of the pattern P1 is limited by the large crystal nucleus, and collapse of the pattern P1 is less likely to occur. It is considered that, due to such a mechanism, even if the thickness T1 of the solidified body 101 is slightly smaller than the height Hp of the pattern P1, the collapse rate of the pattern P1 is reduced.
As described above, when the solidified material 101 is too thick or too thin, the collapse rate of the pattern P1 is reduced. In other words, there is an appropriate range in the thickness of the solidified material 101 in order to reduce the collapse rate of the pattern P1 of the substrate W after drying. For example, if the setting of the setting body 101 to a value within the range described with reference to fig. 9, the collapse rate of the pattern P1 of the substrate W after drying can be reduced. This can dry the substrate W while suppressing the collapse rate of the pattern P1.
Next, measurement results when other samples are used will be described.
Fig. 14 to 16 are tables showing examples of the collapse rate of the pattern P1 obtained when a plurality of samples on which the pattern P1 having the same shape and strength is formed are treated while changing the initial concentration of camphor.
Fig. 14 shows the collapse rate of the pattern P1 when the sublimable substance is camphor and the solvent is IPA, fig. 15 shows the collapse rate of the pattern P1 when the sublimable substance is camphor and the solvent is acetone, and fig. 16 shows the collapse rate of the pattern P1 when the sublimable substance is camphor and the solvent is PGEE.
In the measurement conditions 2-1 to 2-5 shown in FIG. 14, the conditions were the same except for the initial concentration of camphor. Similarly, the conditions other than the initial concentration of camphor are the same in the measurement conditions 3-1 to 3-13 shown in FIG. 15, and the conditions other than the initial concentration of camphor are the same in the measurement conditions 4-1 to 4-8 shown in FIG. 16.
The same samples were used in the measurements of fig. 14 to 16. The intensity of the pattern P1 of the sample used in the measurement of fig. 14 to 16 is different from the intensity of the pattern P1 of the sample used in the measurement of fig. 9. Therefore, although fig. 9 and 14 each show the collapse rate of the pattern P1 when the sublimable substance is camphor and the solvent is IPA, the collapse rates shown in fig. 9 and 14 cannot be easily compared because the patterns P1 used in the measurement have different intensities.
Fig. 17 is a line graph showing a relationship between the concentration of camphor and the collapse rate of the pattern P1 in fig. 14. Fig. 18 is a line graph showing a relationship between the concentration of camphor and the collapse rate of the pattern P1 in fig. 15. Fig. 19 is a line graph showing a relationship between the concentration of camphor and the collapse rate of the pattern P1 in fig. 16.
First, an example of the relationship between the initial concentration of camphor and the collapse rate of the pattern P1 when the solvent is IPA will be described with reference to fig. 14 and 17.
As shown in measurement condition 2-1 of FIG. 14, the collapse rate of pattern P1 was 91.7% when the initial concentration of camphor was 0.89 wt%.
As shown in measurement condition 2-2 of FIG. 14, the collapse rate of pattern P1 was 58.4% at an initial concentration of 0.96% by weight of camphor.
As shown in measurement conditions 2-3 of FIG. 14, the collapse rate of pattern P1 was 37.3% at an initial concentration of 1.13% by weight of camphor.
As shown in measurement conditions 2 to 4 of FIG. 14, the collapse rate of the pattern P1 was 50.6% at an initial concentration of 1.38% by weight of camphor.
As shown in measurement conditions 2 to 5 of FIG. 14, the collapse rate of the pattern P1 was 95.3% when the initial concentration of camphor was 1.55 wt%.
As can be seen from fig. 14 and 17, when the initial concentration of camphor was increased from 0.89wt% to 0.96wt%, the collapse rate of pattern P1 was drastically reduced (measurement condition 2-1→measurement condition 2-2). When the initial concentration of camphor was reduced from 1.55wt% to 1.38wt%, the collapse rate of pattern P1 was also drastically reduced (measurement condition 2-5. Fwdarw. Measurement condition 2-4).
When the initial concentration of camphor is in the range of 0.96wt% or more and 1.38wt% or less, the collapse rate of the pattern P1 is 58.4% or less. Therefore, in the case where the solvent is IPA, the initial concentration of camphor is preferably more than 0.89% by weight and less than 1.55% by weight, more preferably 0.96% by weight or more and 1.38% by weight or less.
Next, an example of the relationship between the initial concentration of camphor and the collapse rate of the pattern P1 when the solvent is acetone will be described with reference to fig. 15 and 18.
As shown in measurement condition 3-3 of FIG. 15, the collapse rate of pattern P1 was 86.6% at an initial concentration of 0.62% by weight of camphor.
As shown in measurement conditions 3 to 4 of FIG. 15, the collapse rate of the pattern P1 was 60.2% at an initial concentration of 0.69wt% of camphor.
As shown in the measurement conditions 3 to 9 of FIG. 15, the collapse rate of the pattern P1 was 99.7% when the initial concentration of camphor was 1.04% by weight.
As shown in measurement conditions 3 to 8 of FIG. 15, the collapse rate of the pattern P1 was 82.2% at an initial concentration of 0.96% by weight of camphor.
As shown in measurement conditions 3 to 7 of FIG. 15, the collapse rate of the pattern P1 was 76.4% at an initial concentration of 0.89% by weight of camphor.
As can be seen from fig. 15 and 18, when the initial concentration of camphor was increased from 0.62wt% to 0.69wt%, the collapse rate of pattern P1 was drastically reduced (measurement condition 3-3→measurement condition 3-4). When the initial concentration of camphor was reduced from 1.04wt% to 0.96wt%, the collapse rate of pattern P1 was also drastically reduced (measurement condition 3-9. Fwdarw. Measurement condition 3-8).
However, when the initial concentration of camphor is in the range of 0.96wt% or more and 1.04wt% or less, the collapse rate of the pattern P1 is not so low. When the initial concentration of camphor was reduced from 0.96wt% to 0.89wt% (measurement condition 3-8→measurement condition 3-7), the collapse rate of pattern P1 was drastically reduced, and the collapse rate of pattern P1 was low. Therefore, in the case where the solvent is acetone, the initial concentration of camphor is preferably more than 0.62wt% and 0.96wt% or less.
Next, an example of the relationship between the initial concentration of camphor and the collapse rate of the pattern P1 when the solvent is PGEE will be described with reference to fig. 16 and 19.
As shown in measurement condition 4-3 of FIG. 16, the collapse rate of pattern P1 was 98.9% at an initial concentration of 3.06wt% of camphor.
As shown in measurement condition 4-4 of FIG. 16, the collapse rate of pattern P1 was 88.3% at an initial concentration of 3.55% by weight of camphor.
As shown in measurement conditions 4 to 5 of FIG. 16, the collapse rate of pattern P1 was 79.4% at an initial concentration of 4.23% by weight of camphor.
As shown in measurement conditions 4 to 8 of FIG. 16, the collapse rate of the pattern P1 was 99.5% at an initial concentration of 9.95% by weight of camphor.
As shown in measurement conditions 4 to 7 of FIG. 16, the collapse rate of the pattern P1 was 62.1% at an initial concentration of 6.86wt% of camphor.
As shown in measurement conditions 4 to 6 of FIG. 16, the collapse rate of pattern P1 was 57.5% at an initial concentration of 5.23% by weight of camphor.
As can be seen from fig. 15 and 18, when the initial concentration of camphor is increased from 3.06wt% to 3.55wt% (measurement condition 4-3→measurement condition 4-4), the collapse rate of pattern P1 is drastically reduced, but when this range is included, the collapse rate of pattern P1 is not too low. When the initial concentration of camphor was increased from 3.55wt% to 4.23wt% (measurement condition 4-4→measurement condition 4-5), the collapse rate of pattern P1 was drastically reduced, and the collapse rate of pattern P1 was low.
Further, when the initial concentration of camphor is reduced from 9.95wt% to 6.86wt% (measurement conditions 4 to 8→measurement conditions 4 to 7), the collapse rate of the pattern P1 is drastically reduced, but when the initial concentration is within this range, the collapse rate of the pattern P1 may not be too low. That is, when the initial concentration of camphor is around 6.86wt%, the collapse rate of the pattern P1 is low, but when the initial concentration of camphor is around 9.95wt%, the collapse rate of the pattern P1 is high.
When the initial concentration of camphor was reduced from 6.86wt% to 5.23wt% (measurement condition 4-7. Fwdarw. Measurement condition 4-6), the collapse rate of pattern P1 was gradually reduced. Therefore, in the case where the solvent is PGEE, the initial concentration of camphor is preferably more than 3.55wt% and 6.86wt% or less.
Fig. 20 is a graph obtained by overlapping the folding lines of fig. 17 to 19. In fig. 20, the broken line (IPA) of fig. 17 is shown by a solid line, the broken line (acetone) of fig. 18 is shown by a broken line, and the broken line (PGEE) of fig. 19 is shown by a one-dot chain line.
In the case where the solvent was IPA, the collapse rate of the pattern P1 was at a minimum of 37.3% at an initial concentration of 1.13% by weight of camphor (measurement conditions 2-3).
In the case where the solvent is acetone, the collapse rate of the pattern P1 is 57.6% at an initial concentration of 0.78wt% of camphor (measurement conditions 3 to 5).
In the case of PGEE as the solvent, the collapse rate of pattern P1 was 57.5% at an initial concentration of 5.23% by weight of camphor (measurement conditions 4-6).
In other words, the initial concentration of camphor when the collapse rate of the pattern P1 is the lowest is 0.78wt% in the case of acetone, 1.13wt% in the case of IPA, and 5.23wt% in the case of PGEE. When these solvents are compared, the initial concentration of camphor increases with decreasing vapor pressure of the solvent when the collapse rate of the pattern P1 is the lowest. That is, if the solvent is easily evaporated, the concentration of the sublimating substance contained in the treatment liquid before drying does not necessarily have to be high. Conversely, if the solvent is difficult to evaporate, the concentration of the sublimating substance contained in the pretreatment liquid before drying must be made high.
In the present invention, since it is necessary to evaporate the solvent from the pretreatment liquid before drying to form the solidified material 101 containing the sublimate on the surface of the substrate W, a step of selecting the solvent according to the vapor pressure of the sublimate can be performed, for example.
As described above, according to the measurement result of fig. 9, if the initial concentration of camphor is set to a value within the preferable range, the intercalation rate is also automatically set to a value within the preferable range. Therefore, it is considered that, in the measurement of fig. 14 to 16, if the initial concentration of camphor is set to a value within the preferable range, the insertion rate is also automatically set to a value within the preferable range. Thus, the collapse rate of the pattern P1 is considered to be reduced.
However, it is considered that the initial concentration of camphor is set to a value within a preferable range according to the shape and strength of the pattern P1, but the embedding rate is not necessarily set to a value within a preferable range. Similarly, it is considered that, depending on the shape and strength of the pattern P1, the embedding rate is set to a value within a preferable range, but the initial concentration of camphor is not necessarily set to a value within a preferable range.
As described above, in embodiment 1, the pre-drying treatment liquid containing the sublimating substance corresponding to the solute and the solvent is supplied to the surface of the substrate W on which the pattern P1 is formed. Then, the solvent was evaporated from the pre-drying treatment liquid. Thereby, a solidified body 101 containing a sublimating substance is formed on the surface of the substrate W. Then, the solidified material 101 on the substrate W is changed to a gas without passing through a liquid. Thereby, the solidified material 101 is removed from the surface of the substrate W. Therefore, the collapse rate of the pattern P1 can be reduced as compared with conventional drying methods such as spin drying.
When the solvent is evaporated from the drying pretreatment liquid, a solidified material 101 containing a sublimating substance is formed on the surface of the substrate W. The embedding rate at the point in time when the solidified body 101 is formed exceeds 76 and is less than 219. As described above, when the embedding rate is outside this range, the collapse number of the pattern P1 increases according to the intensity of the pattern P1. Conversely, if the embedding rate is within this range, the collapse number of the pattern P1 can be reduced even if the strength of the pattern P1 is low. Therefore, even if the strength of the pattern P1 is low, the collapse rate of the pattern P1 can be reduced.
Next, embodiment 2 will be described.
The main points of difference between embodiment 2 and embodiment 1 are: the pretreatment liquid before drying contains a sublimable substance and a solvent, and also contains an adsorbent substance.
In fig. 21 to 23F below, the same reference numerals as those in fig. 1 and the like are given to the same components as those in fig. 1 to 20, and the description thereof is omitted.
Fig. 21 is a schematic view of the inside of the processing unit 2 included in the substrate processing apparatus 1 according to embodiment 2 as viewed horizontally.
The plurality of nozzles of the processing unit 2 further includes a 2 nd chemical nozzle 31B that ejects a chemical different from the chemical ejected from the chemical nozzle 31 (which corresponds to the 1 st chemical nozzle) toward the upper surface of the substrate W. The 2 nd chemical liquid nozzle 31B may be a scanning nozzle horizontally movable in the chamber 4 or may be a fixed nozzle fixed to the partition wall 5 of the chamber 4. Fig. 21 shows an example in which the 2 nd chemical liquid nozzle 31B is a scanning nozzle.
The 2 nd chemical liquid nozzle 31B is connected to a 2 nd chemical liquid pipe 32B that guides the chemical liquid to the 2 nd chemical liquid nozzle 31B. When the 2 nd chemical valve 33B attached to the 2 nd chemical pipe 32B is opened, the chemical is continuously discharged downward from the discharge port of the 2 nd chemical nozzle 31B. The chemical liquid discharged from the 2 nd chemical liquid nozzle 31B may be a liquid containing at least one of sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, acetic acid, ammonia water, aqueous hydrogen peroxide, an organic acid (e.g., citric acid, oxalic acid, etc.), an organic base (e.g., TMAH: tetramethylammonium hydroxide, etc.), a surfactant, and an anticorrosive, as long as it is different from the type of chemical liquid discharged from the chemical liquid nozzle 31.
The 2 nd chemical liquid nozzle 31B is connected to a nozzle moving unit 34B that moves the 2 nd chemical liquid nozzle 31B in at least one of the vertical direction and the horizontal direction. The nozzle moving unit 34B horizontally moves the 2 nd chemical nozzle 31B between a processing position where the chemical ejected from the 2 nd chemical nozzle 31B is supplied to the upper surface of the substrate W and a standby position where the 2 nd chemical nozzle 31B is located around the processing cup 21 in a plan view.
As described above, the pretreatment liquid before drying contains an adsorbent in addition to the sublimate and the solvent. The pre-drying treatment liquid is a solution containing a sublimate corresponding to a solute, a solvent miscible with the sublimate, and an adsorbent adsorbed on the surface of the pattern P1 (see fig. 23A). The sublimating substance, the solvent and the adsorbing substance are substances different from each other in kind. The adsorption substance is a substance that is miscible with at least one of the sublimating substance and the solvent.
The solvent is a liquid of a dissolved substance that is miscible with the sublimating substance. The concentration of the dissolved substance in the pre-drying treatment liquid is higher than the concentration of the sublimating substance in the pre-drying treatment liquid and higher than the concentration of the adsorbing substance in the pre-drying treatment liquid. The concentration of the adsorbent in the pre-drying treatment liquid may be the same as or different from the concentration of the sublimate in the pre-drying treatment liquid.
The adsorbed substance is an amphiphilic molecule containing both hydrophilic and hydrophobic groups. The adsorbent material may be a surfactant. The adsorbent may be any substance having a different type from the sublimating substance and the solvent, and may be a substance (substance having sublimating property) which changes from a solid to a gas without passing through a liquid at normal temperature or normal pressure, or may be a substance different from the sublimating substance. The sublimating substance may be a hydrophobic substance or a hydrophilic substance, or may be an amphiphilic molecule. Similarly, the solvent may be a hydrophobic substance or a hydrophilic substance, or may be an amphiphilic molecule.
In the case where the sublimating substance is a hydrophilic substance or an amphiphilic molecule, the adsorbed substance may be more hydrophilic than the sublimating substance. In other words, the solubility of the adsorbed species in water may be higher than the solubility of the sublimating species in water. In the case where the sublimating substance is a hydrophobic substance or an amphiphilic molecule, the sublimating substance may be more hydrophobic than the adsorbing substance. In other words, the solubility of the sublimating substance in the oil may be higher than the solubility of the adsorbing substance in the oil. These are also the same for solvents.
When the surface of the pattern P1 is hydrophilic and the adsorption material is more hydrophilic than the sublimation material, the adsorption material is more likely to be adsorbed on the surface of the pattern P1 than the sublimation material. Hydrophilic groups of the adsorbed substance are attached to the surface of the pattern P1, and the sublimated substance is attached to hydrophobic groups of the adsorbed substance attached to the surface of the pattern P1. When the surface of the pattern P1 is hydrophobic and the sublimate is more hydrophobic than the adsorbent, the sublimate is more likely to be adsorbed on the surface of the pattern P1 than the adsorbent. Therefore, the sublimating substance can be positioned on or near the surface of the pattern P1 regardless of whether the surface of the pattern P1 is hydrophilic or hydrophobic.
The freezing point of the sublimating substance is higher than room temperature. The sublimating material may have a freezing point higher than the boiling point of the solvent. The freezing point of the solvent is below room temperature. The solidification point of the adsorbent may be room temperature or may be different from room temperature. In the case where the solidification point of the adsorbent is higher than room temperature, the solidification point of the adsorbent may be the same as or different from the solidification point of the sublimating substance. The solidification point of the treatment liquid before drying was lower than room temperature (a value at or near 23 ℃). The solidification point of the pretreatment liquid before drying may be not less than room temperature.
The vapor pressure of the solvent is higher than the vapor pressure of the sublimating substance and higher than the vapor pressure of the adsorbing substance. The vapor pressure of the adsorption material may be the same as the vapor pressure of the sublimation material or may be different from the vapor pressure of the sublimation material. The solvent evaporates from the pre-drying treatment liquid at an evaporation rate greater than the evaporation rates of the sublimating substance and the adsorbing substance. The freezing point of the treatment liquid before drying rises with the evaporation of the solvent. When the solidification point of the pretreatment liquid rises to room temperature, the pretreatment liquid changes from liquid to solid. Thereby, the solidified material 101 containing the sublimating substance is formed.
Hereinafter, examples of the sublimable substance being camphor, the solvent being IPA, and the adsorptive substance being t-butanol will be described. In the following description, the pretreatment liquid before drying is a solution of camphor, IPA, and t-butanol. Naphthalene may be contained in the pretreatment liquid before drying instead of camphor. Instead of IPA, acetone or PGEE may be contained in the pretreatment liquid before drying. Instead of t-butanol, cyclohexanol may be contained in the pretreatment liquid before drying.
The camphor contains a hydrocarbon group as a hydrophobic group and a carbonyl group as a hydrophilic group in the molecule. The molecule of IPA contains an alkyl group as a hydrophobic group and a hydroxyl group as a hydrophilic group. The tertiary butanol also contains an alkyl group as a hydrophobic group and a hydroxyl group as a hydrophilic group in the molecule. IPA and tert-butanol are amphiphilic molecules. Strictly speaking, camphor is an amphiphilic molecule, but is much less soluble in water than t-butanol and therefore can be considered as a hydrophobic substance. Camphor is more hydrophobic than t-butanol.
The 1 st tank 87A and the 2 nd tank 87B shown in fig. 3 store drying pretreatment liquids having the same concentration of the adsorbed substances and different concentrations of the sublimated substances. Therefore, even if the pre-drying treatment liquid supplied from the 1 st tank 87A is mixed with the pre-drying treatment liquid supplied from the 2 nd tank 87B, the concentration of the adsorbent in the mixed pre-drying treatment liquid does not change from the concentrations of the adsorbent in the pre-drying treatment liquids in the 1 st tank 87A and the 2 nd tank 87B. The initial concentrations of the sublimates in the treatment liquid before drying in the 1 st tank 87A and the 2 nd tank 87B may be set to the same value as in embodiment 1 or may be set to a different value from embodiment 1.
Next, an example of the processing of the substrate W according to embodiment 2 will be described.
Fig. 22 is a process diagram for explaining an example of processing of the substrate W according to embodiment 2. Hereinafter, refer to fig. 21 and 22.
In an example of the processing of the substrate W according to embodiment 2, steps S3-1 to S4-2 shown in fig. 22 are performed instead of steps S3 to S4 shown in fig. 5. The steps other than these are the same as steps S1 to S2 and steps S5 to S11 shown in fig. 5. Therefore, the following description will be given of steps S3-1 to S4-2.
Hereinafter, an example in which hydrofluoric acid and SC1 (a mixture of ammonia, hydrogen peroxide and water) are sequentially supplied to a silicon wafer corresponding to the substrate W will be described. The natural oxide film formed on the silicon wafer is removed from the silicon wafer by supplying hydrofluoric acid. Thereby, silicon is exposed on the surface of the pattern P1. Then, SC1 is supplied to the silicon wafer. The silicon exposed on the surface of the pattern P1 changes to silicon oxide due to contact with SC1. Thereby, the surface of the pattern P1 changes from hydrophobic to hydrophilic. Therefore, when the surface of the pattern P1 is hydrophilic, the pretreatment liquid before drying is supplied to the silicon wafer.
As shown in fig. 22, after the rotation of the substrate W is started (step S2 in fig. 22), the 1 st chemical solution supplying step (step S3-1 in fig. 22) is performed, that is, hydrofluoric acid as an example of the chemical solution is supplied to the upper surface of the substrate W, and a liquid film of hydrofluoric acid covering the entire upper surface of the substrate W is formed.
Specifically, the nozzle moving unit 34 moves the chemical nozzle 31 from the standby position to the processing position in a state where the blocking member 51 is located at the upper position and the at least one shield 24 is located at the upper position. Then, the chemical liquid valve 33 is opened, and the chemical liquid nozzle 31 starts to discharge hydrofluoric acid. When a predetermined time has elapsed since the chemical solution valve 33 was opened, the chemical solution valve 33 is closed, and the discharge of hydrofluoric acid is stopped. Then, the nozzle moving unit 34 moves the chemical nozzle 31 to the standby position.
The hydrofluoric acid discharged from the chemical nozzle 31 collides with the upper surface of the substrate W rotated at the liquid supply speed, and then flows outward along the upper surface of the substrate W by centrifugal force. Thus, hydrofluoric acid is supplied to the entire upper surface of the substrate W, and a liquid film of hydrofluoric acid is formed to cover the entire upper surface of the substrate W. When the chemical solution nozzle 31 ejects the hydrofluoric acid, the nozzle moving unit 34 may move the deposition position so that the hydrofluoric acid passes through the central portion and the outer peripheral portion with respect to the deposition position on the upper surface of the substrate W, or may rest the deposition position at the central portion.
Next, a 1 st rinse liquid supply step (step S4-1 in fig. 22) is performed in which pure water as an example of a rinse liquid is supplied to the upper surface of the substrate W, thereby washing away hydrofluoric acid on the substrate W.
Specifically, the nozzle moving unit 38 moves the rinse liquid nozzle 35 from the standby position to the treatment position in a state where the blocking member 51 is located at the upper position and the at least one shield 24 is located at the upper position. Then, the rinse liquid valve 37 is opened, and the rinse liquid nozzle 35 starts to discharge the rinse liquid. Before starting the ejection of the pure water, the shield elevating unit 27 may vertically move at least one shield 24 in order to switch the shield 24 blocking the liquid discharged from the substrate W. When a predetermined time has elapsed since the opening of the rinse liquid valve 37, the rinse liquid valve 37 is closed, and the discharge of the rinse liquid is stopped. Then, the nozzle moving unit 38 moves the rinse liquid nozzle 35 to the standby position.
After the pure water discharged from the rinse liquid nozzle 35 collides with the upper surface of the substrate W rotated at the liquid supply speed, the pure water moves to the outside along the upper surface of the substrate W by centrifugal force. The hydrofluoric acid on the substrate W is replaced with pure water ejected from the rinse liquid nozzle 35. Thereby, a liquid film of pure water is formed which covers the entire upper surface of the substrate W. When the rinse liquid nozzle 35 ejects the deionized water, the nozzle moving means 38 may move the deionized water so as to pass through the center portion and the outer peripheral portion with respect to the deionized water on the upper surface of the substrate W, or may rest the deionized water on the center portion.
Next, a 2 nd chemical supply step (step S3-2 in fig. 22) of supplying SC1, which is an example of the chemical, to the upper surface of the substrate W is performed, thereby forming a liquid film of SC1 covering the entire upper surface of the substrate W.
Specifically, the nozzle moving unit 34B moves the 2 nd chemical nozzle 31B from the standby position to the processing position in a state where the blocking member 51 is located at the upper position and the at least one shield 24 is located at the upper position. Then, the 2 nd chemical liquid valve 33B is opened, and the 2 nd chemical liquid nozzle 31B starts ejecting SC1. When a predetermined time has elapsed since the 2 nd chemical solution valve 33B was opened, the 2 nd chemical solution valve 33B is closed, and the ejection of SC1 is stopped. Then, the nozzle moving unit 34B moves the 2 nd chemical nozzle 31B to the standby position.
The SC1 discharged from the 2 nd chemical nozzle 31B collides with the upper surface of the substrate W rotated at the liquid supply speed, and then flows outward along the upper surface of the substrate W by centrifugal force. The pure water on the substrate W is replaced with SC1 discharged from the 2 nd chemical nozzle 31B. Thereby, a liquid film of SC1 covering the entire upper surface of the substrate W is formed. When the 2 nd chemical nozzle 31B ejects SC1, the nozzle moving means 34B may move the landing position so that the SC1 passes through the central portion and the outer peripheral portion with respect to the landing position on the upper surface of the substrate W, or may rest the landing position at the central portion.
Next, a 2 nd rinse liquid supply step (step S4-2 in fig. 22) is performed, in which pure water as an example of a rinse liquid is supplied to the upper surface of the substrate W, thereby washing SC1 on the substrate W.
Specifically, the nozzle moving unit 38 moves the rinse liquid nozzle 35 from the standby position to the treatment position in a state where the blocking member 51 is located at the upper position and the at least one shield 24 is located at the upper position. Then, the rinse liquid valve 37 is opened, and the rinse liquid nozzle 35 starts to discharge the rinse liquid. Before starting the ejection of the pure water, the shield elevating unit 27 may vertically move at least one shield 24 in order to switch the shield 24 blocking the liquid discharged from the substrate W. When a predetermined time has elapsed since the opening of the rinse liquid valve 37, the rinse liquid valve 37 is closed, and the discharge of the rinse liquid is stopped. Then, the nozzle moving unit 38 moves the rinse liquid nozzle 35 to the standby position.
The pure water discharged from the rinse liquid nozzle 35 collides with the upper surface of the substrate W rotated at the liquid supply speed, and then flows outward along the upper surface of the substrate W by centrifugal force. SC1 on the substrate W is replaced with pure water ejected from the rinse liquid nozzle 35. Thereby, a liquid film of pure water is formed which covers the entire upper surface of the substrate W. When the rinse liquid nozzle 35 ejects the deionized water, the nozzle moving means 38 may move the deionized water so as to pass through the center portion and the outer peripheral portion with respect to the deionized water on the upper surface of the substrate W, or may rest the deionized water on the center portion.
After the 2 nd rinse liquid supply step (step S4-2 in fig. 22), a substitution liquid and a pre-drying treatment liquid are sequentially supplied to the substrate W (step S5 to step S6 in fig. 22) and the solidified material 101 (see fig. 23E) on the surface of the substrate W is sublimated (step S7 to step S9 in fig. 22) similarly to the example of the treatment of the substrate W according to embodiment 1 shown in fig. 5. Then, the substrate W is carried out of the chamber 4 (steps S10 to S11 in fig. 22). Thereby, the processed substrate W is carried out of the chamber 4.
Next, a phenomenon that is supposed to occur on the surface of the pattern P1 to which the pre-drying treatment liquid is supplied will be described.
Fig. 23A to 23F are cross-sectional views of a substrate W for explaining the same phenomenon. In fig. 23A to 23E, t-butanol is denoted as TBA. In fig. 23A to 23C, the hydrophilic group of the tertiary butanol molecule is indicated by a thick straight line, and the hydrophobic group of the tertiary butanol molecule is indicated by a black dot.
As described above, in the example of the processing of the substrate W according to embodiment 2, hydrofluoric acid and SC1 are sequentially supplied to the silicon wafer corresponding to the substrate W. The surface of the pattern P1 changes to be hydrophobic due to the supply of hydrofluoric acid. Then, the surface of the pattern P1 changes to hydrophilic due to the supply of SC 1. Therefore, the pre-drying treatment liquid containing camphor, IPA and t-butanol is supplied to the silicon wafer when the surface of the pattern P1 is hydrophilic.
Camphor is a substance considered to be hydrophobic, and tertiary butanol is an amphiphilic molecule comprising a hydrophilic group and a hydrophobic group. As shown in fig. 23A, the surface of the pattern P1 is hydrophilic, and thus the hydrophilic group of the tertiary butanol molecule is attracted to the surface of the pattern P1. Thus, as shown in fig. 23B, the hydrophilic group of the tertiary butanol molecule is adsorbed to the surface of the pattern P1, and the tertiary butanol thin film is formed on the side surface Ps and the upper surface Pu of the pattern P1.
Fig. 23B shows an example of a monomolecular film in which t-butanol is formed along the surface of pattern P1. As shown in fig. 23C, in the case of this example, the hydrophobic group of the camphor molecule is attached to the hydrophobic group of the tertiary butanol molecule adsorbed on the surface of the pattern P1. In the case of the laminated film in which t-butanol is formed along the surface of the pattern P1, the hydrophobic group of the camphor molecule is attached to the hydrophobic group of the t-butanol molecule exposed at the surface layer of the laminated film. Thus, camphor is held on the surface of the pattern P1 through the thin film of t-butanol.
As shown in fig. 23C, camphor molecules in the drying pretreatment liquid are attached to camphor molecules held on the tertiary butanol film. By this phenomenon, a large amount of camphor molecules are held on the side Ps of the pattern P1 via the molecular layer of t-butanol. Accordingly, as shown in fig. 23D, a sufficient amount of camphor molecules enter between the patterns P1. Fig. 23D shows an example in which a thin film of t-butanol is formed not only on the side surface Ps and the upper surface Pu of the pattern P1 but also on the bottom surface Pb of the recess formed between 2 adjacent patterns P1.
IPA, which corresponds to a solvent, evaporates from the pre-drying treatment liquid in a state where a thin film of t-butanol is formed along the surface of the pattern P1 and a plurality of camphor molecules are held on the surface of the pattern P1 through the thin film of t-butanol. The solidification point of the treatment liquid rises with the evaporation of IPA, and the concentrations of camphor and tert-butanol rise. Thus, as shown in fig. 23E, a solidified body 101 containing camphor and tert-butanol is formed on the surface of the substrate W. Then, as shown in fig. 23F, the solidified body 101 is gasified, so that it is removed from the surface of the substrate W.
According to the study of the inventors of the present application, it was confirmed that: when the substrate W according to embodiment 2 is processed using a silicon plate-like sample on which the pattern P1 is formed instead of the substrate W, if a solution of camphor, IPA, and t-butanol is used as the pre-drying treatment liquid, the collapse rate of the pattern P1 is reduced compared to the case where a solution of camphor and IPA is used as the pre-drying treatment liquid. When the concentration of t-butanol (volume percent concentration) was changed within the range of 0.1vol% to 10vol%, no large difference in the collapse rate of pattern P1 was observed. Therefore, if t-butanol is added, the collapse rate of the pattern P1 is reduced even in a small amount. The concentration of t-butanol may be within the above range or may be outside the above range.
In embodiment 2, in addition to the effects of embodiment 1, the following effects can be obtained. Specifically, in embodiment 2, a pre-drying treatment liquid containing an adsorption substance in addition to a sublimating substance and a solvent is supplied to the surface of the substrate W on which the pattern P1 is formed. Then, the solvent was evaporated from the pre-drying treatment liquid. Thereby, a solidified body 101 containing a sublimating substance is formed on the surface of the substrate W. Then, the solidified material 101 on the substrate W is changed to a gas without passing through a liquid. Thereby, the solidified material 101 is removed from the surface of the substrate W. Therefore, the collapse rate of the pattern P1 can be reduced as compared with conventional drying methods such as spin drying.
The sublimating substance is a substance containing a hydrophobic group in a molecule. The adsorption material is a material containing a hydrophobic group and a hydrophilic group in a molecule. The hydrophilic nature of the adsorbed material is higher than the hydrophilic nature of the sublimating material. When the surface of the pattern P1 is either hydrophilic or hydrophobic, or the surface of the pattern P1 includes a hydrophilic portion and a hydrophobic portion, the adsorbing substance in the pretreatment liquid before drying is adsorbed on the surface of the pattern P1.
Specifically, when the surface of the pattern P1 is hydrophilic, hydrophilic groups of the adsorbed substance in the pretreatment liquid before drying adhere to the surface of the pattern P1, and hydrophobic groups of the sublimated substance in the pretreatment liquid before drying adhere to the hydrophobic groups of the adsorbed substance. Thereby, the sublimating substance is held on the surface of the pattern P1 through the adsorbing substance. In the case where the surface of the pattern P1 is hydrophobic, at least a hydrophobic group of the sublimating substance adheres to the surface of the pattern P1. Therefore, when the surface of the pattern P1 is either hydrophilic or hydrophobic, or the surface of the pattern P1 includes a hydrophilic portion and a hydrophobic portion, the sublimating substance is held on or near the surface of the pattern P1 before the solvent is evaporated.
When the sublimating substance is hydrophilic and the surface of the pattern P1 is hydrophilic, the sublimating substance is attracted to the surface of the pattern P1 by electrostatic attraction. On the other hand, when the sublimating substance is hydrophobic and the surface of the pattern P1 is hydrophilic, such attractive force is weak or does not occur, and therefore, the sublimating substance is difficult to adhere to the surface of the pattern P1. In addition, when the sublimating substance is hydrophobic, the surface of the pattern P1 is hydrophilic, and the space between the patterns P1 is extremely narrow, it is considered that a sufficient amount of the sublimating substance does not enter between the patterns P1. These phenomena occur also when the sublimating substance is hydrophilic and the surface of the pattern P1 is hydrophobic.
When the solvent is evaporated in a state where the surface of the pattern P1 or the vicinity thereof is free from the sublimating substance, a collapse force is applied to the pattern P1 from the solvent in contact with the surface of the pattern P1, and the pattern P1 may collapse. It is also considered that when the solvent is evaporated in a state where there is no sufficient amount of the sublimating substance between the patterns P1, the gaps between the patterns P1 are not buried by the solidified material 101, and the patterns P1 collapse. If the sublimating substance is disposed on or near the surface of the pattern P1 before the solvent is evaporated, such collapse can be reduced. This can reduce the collapse rate of the pattern P1.
In embodiment 2, not only the sublimation material but also the adsorption material has sublimation property. The adsorptive substance changes from solid to gas at normal temperature or normal pressure without passing through liquid. When at least a part of the surface of the pattern P1 is hydrophilic, the solvent is evaporated in a state where the adsorbing substance in the pre-drying treatment liquid is adsorbed on the surface of the pattern P1. The adsorbed species change from liquid to solid at the surface of pattern P1. Thereby, a solidified body 101 containing the adsorbed substance and the sublimated substance is formed. Then, the solid of the adsorbed substance is changed to a gas at the surface of the pattern P1 without passing through the liquid. Therefore, the collapsing force can be reduced as compared with the case where the liquid is gasified at the surface of the pattern P1.
In embodiment 2, a drying pretreatment liquid having a low concentration of an adsorbent is supplied to the surface of the substrate W. When at least a part of the surface of the pattern P1 is hydrophilic, the hydrophilic group of the adsorbing substance adheres to the surface of the pattern P1, and a monomolecular film of the adsorbing substance is formed along the surface of the pattern P1. When the concentration of the adsorbed substance is high, a plurality of monolayers are stacked to form a stacked film of the adsorbed substance along the surface of the pattern P1. In this case, the sublimating substance is held on the surface of the pattern P1 through the laminated film of the adsorbing substance. When the thickness of the layer of the adsorbed substance is set to be smaller, the sublimated substance entering between the patterns P1 is reduced. Therefore, by reducing the concentration of the adsorbed substance, more sublimating substance can be made to enter between the patterns P1.
In embodiment 2, a pre-drying treatment liquid containing a sublimating substance having a higher hydrophobicity than the adsorbing substance is supplied to the surface of the substrate W. Since both the sublimating substance and the adsorbing substance include hydrophobic groups, both the sublimating substance and the adsorbing substance can be attached to the surface of the pattern P1 when at least a portion of the surface of the pattern P1 is hydrophobic. However, the affinity of the sublimating substance with the pattern P1 is higher than that of the adsorbing substance with the pattern P1, and therefore, more sublimating substance adheres to the surface of the pattern P1 than the adsorbing substance. This allows more sublimating substances to adhere to the surface of the pattern P1.
Other embodiments
The present invention is not limited to the above embodiments, and various modifications can be made.
For example, in order to change the thickness T1 of the solidified body 101, conditions other than the concentration of the treatment liquid before drying may be changed. For example, the temperature of the pre-drying treatment liquid may be changed in addition to or instead of the concentration of the pre-drying treatment liquid.
The pattern P1 is not limited to a single-layer structure, and may be a laminated structure. At least a portion of the pattern P1 may be formed of a material other than silicon. For example, at least a portion of the pattern P1 may be formed of metal.
In an example of the processing of the substrate W according to embodiments 1 and 2, in order to maintain the pre-drying processing liquid on the substrate W as a liquid, a temperature maintaining step of maintaining the pre-drying processing liquid on the substrate W at a liquid maintaining temperature higher than the freezing point of the pre-drying processing liquid and lower than the boiling point of the pre-drying processing liquid may be performed.
In the case where the rinse liquid on the substrate W such as pure water can be replaced with the pre-drying treatment liquid, the pre-drying treatment liquid supplying step may be performed without performing the replacement liquid supplying step of replacing the rinse liquid on the substrate W with the replacement liquid.
In an example of the processing of the substrate W according to embodiment 2, the surface of the pattern P1 may be hydrophilic from the beginning, that is, from the time before the substrate is carried into the substrate processing apparatus 1. In this case, the 2 nd chemical liquid supply step (step S3-2 in fig. 22) and the 2 nd rinse liquid supply step (step S4-2 in fig. 22) may be omitted. In the 1 st chemical supply step (step S3-1 in fig. 22), the chemical supplied to the substrate W may be other than hydrofluoric acid.
In an example of the process of the substrate W according to embodiment 2, when the pre-drying process liquid is supplied to the surface of the substrate W, the surface of the pattern P1 may be hydrophobic. In this case, the surface of the pattern P1 may be hydrophobic from the beginning, or may be changed to be hydrophobic when the substrate W is processed.
In embodiment 2, if the initial concentration of the sublimating substance (concentration of the sublimating substance in the pre-drying treatment liquid before being supplied to the substrates W) is not changed, one of the 1 st tank 87A and the 2 nd tank 87B shown in fig. 3 may be omitted.
In embodiment 2, the adsorbent may be mixed with the solution of the sublimating substance and the solvent outside the 1 st tank 87A and the 2 nd tank 87B. In this case, the adsorbent may be mixed before the solution of the sublimate and the solvent is discharged from the pre-drying treatment liquid nozzle 39, or may be mixed after the solution of the sublimate and the solvent is discharged from the pre-drying treatment liquid nozzle 39. In the latter case, the adsorbent may be mixed into the solution of the sublimating substance and the solvent in the space between the drying pretreatment liquid nozzle 39 and the substrate W, or may be mixed into the solution of the sublimating substance and the solvent on the upper surface of the substrate W.
The blocking member 51 may include a cylindrical portion extending downward from the outer peripheral portion of the circular plate portion 52, in addition to the circular plate portion 52. In this case, when the blocking member 51 is disposed at the lower position, the substrate W held by the spin chuck 10 is surrounded by the cylindrical portion.
The blocking member 51 is rotatable about the rotation axis A1 together with the spin chuck 10. For example, the blocking member 51 may be placed on the spin base 12 in such a manner as not to contact the substrate W. In this case, since the blocking member 51 is coupled to the rotation base 12, the blocking member 51 rotates at the same speed in the same direction as the rotation base 12.
The blocking member 51 may be omitted. However, in the case of supplying a liquid such as pure water to the lower surface of the substrate W, the blocking member 51 is preferably provided. The reason for this is that the liquid drops which have wound around the upper surface of the substrate W from the lower surface of the substrate W along the outer peripheral surface of the substrate W and the liquid drops which have bounced back to the inner side from the processing cup 21 can be blocked by the blocking member 51, and the liquid mixed into the pre-drying processing liquid on the substrate W can be reduced.
The substrate processing apparatus 1 is not limited to an apparatus for processing a disk-shaped substrate W, and may be an apparatus for processing a polygonal substrate W.
The substrate processing apparatus 1 is not limited to a single-wafer apparatus, and may be a batch apparatus for processing a plurality of substrates W at once.
Two or more of the foregoing all the configurations may be combined. Two or more of the foregoing all steps may be combined.
The pre-drying treatment liquid nozzle 39 is an example of a pre-drying treatment liquid supply means. The center nozzle 55 and the rotary motor 14 are examples of a solidification forming unit. The center nozzle 55 and the rotary motor 14 are also examples of sublimation units.
Although the embodiments of the present invention have been described in detail, they are merely specific examples used to explain the technical content of the present invention, and the present invention should not be limited to these specific examples, but the gist and scope of the present invention are not limited to the appended claims.
Claims (6)
1. A substrate processing method comprising the steps of:
a pre-drying treatment liquid supply step of supplying a pre-drying treatment liquid, which is a solution containing a sublimate substance that changes to a gas without passing through a liquid and a solvent that is mutually soluble in the sublimate substance, to a surface of a substrate on which a pattern is formed;
a solidification body formation step of forming a solidification body containing the sublimating substance on the surface of the substrate by evaporating the solvent from the pre-drying treatment liquid on the surface of the substrate; and
a sublimation step of removing the solidified material from the surface of the substrate by sublimating the solidified material,
wherein a value obtained by multiplying a ratio of a thickness of the solidified material formed in the solidified material forming step to a height of the pattern by one hundred is 102 or more and 138 or less.
2. The substrate processing method according to claim 1, wherein the sublimating substance comprises at least one of camphor and naphthalene.
3. The substrate processing method according to claim 1 or 2, wherein the solvent comprises at least one of IPA (isopropyl alcohol), acetone, and PGEE (propylene glycol monoethyl ether).
4. The substrate processing method according to claim 3, wherein,
The solvent is IPA,
the mass percentage concentration of the sublimating substances in the drying pretreatment liquid exceeds 0.62 and is less than 2.06.
5. The substrate processing method according to claim 3, wherein,
the solvent is acetone, and the solvent is acetone,
the concentration of the sublimating substance in the pretreatment liquid exceeds 0.62 and is not more than 0.96 by mass.
6. The substrate processing method according to claim 3, wherein,
the solvent is PGEE,
the concentration of the sublimating substance in the pretreatment liquid exceeds 3.55 and is less than 6.86 by mass.
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| JP2019050214A JP7286359B2 (en) | 2018-06-22 | 2019-03-18 | Substrate processing method, substrate processing apparatus, and pre-drying treatment liquid |
| JP2019-050214 | 2019-03-18 | ||
| CN201910544595.XA CN110634769B (en) | 2018-06-22 | 2019-06-21 | Substrate processing method, substrate processing apparatus, and pre-drying treatment liquid |
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| JP7419163B2 (en) | 2020-05-29 | 2024-01-22 | 株式会社Ｓｃｒｅｅｎホールディングス | Substrate processing device, substrate processing method, learning data generation method, learning method, learning device, learned model generation method, and learned model |
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| JP2022148452A (en) | 2021-03-24 | 2022-10-06 | 株式会社Ｓｃｒｅｅｎホールディングス | Substrate processing method and processing liquid |
| JP2023020501A (en) * | 2021-07-30 | 2023-02-09 | 株式会社Ｓｃｒｅｅｎホールディングス | Substrate processing method and substrate processing apparatus |
| JP2023046629A (en) | 2021-09-24 | 2023-04-05 | 株式会社Ｓｃｒｅｅｎホールディングス | Polishing head and polishing device including the same as well as substrate processing device |
| JP2023046627A (en) | 2021-09-24 | 2023-04-05 | 株式会社Ｓｃｒｅｅｎホールディングス | Substrate processing method, substrate processing apparatus, and process liquid |
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| JP6022829B2 (en) * | 2012-07-03 | 2016-11-09 | 株式会社Ｓｃｒｅｅｎホールディングス | Substrate drying method and substrate drying apparatus |
| JP6216188B2 (en) * | 2013-09-04 | 2017-10-18 | 株式会社Ｓｃｒｅｅｎホールディングス | Substrate drying apparatus and substrate drying method |
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| JP6275578B2 (en) * | 2014-07-30 | 2018-02-07 | 株式会社東芝 | Processing apparatus, processing method, and electronic device manufacturing method |
| JP2015092619A (en) * | 2015-01-08 | 2015-05-14 | 東京エレクトロン株式会社 | Substrate drying method and substrate processing apparatus |
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| WO2018030516A1 (en) * | 2016-08-12 | 2018-02-15 | 東京エレクトロン株式会社 | Substrate processing device, substrate processing method, and storage medium |
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