TW201703875A - Resist liquid storage container, resist liquid supplying device, resist liquid coating device, resist liquid storage device, and method of manufacturing a mask blank - Google Patents

Abstract

A resist liquid storage container (1) includes a flexible bag portion (2) having a containing portion (2a) storing a resist liquid, an injection tube (9) communicating with the containing portion (2a) and adapted to inject the resist liquid, and a discharge pipe (8) communicating with the containing portion (2a) and adapted to discharge the resist liquid to the outside of the resist liquid storage container (1).

Description

Photoresist liquid storage container, photoresist liquid supply device, photoresist liquid application device, photoresist liquid storage device, and method for manufacturing blank mask

The present invention relates to a photoresist liquid storage container for storing a photoresist liquid used for pattern formation of photolithography, a photoresist liquid supply device for supplying a photoresist liquid from a photoresist liquid storage container, and receiving from a photoresist liquid supply device A photoresist liquid coating device that applies a photoresist solution to a substrate or the like, a photoresist liquid storage device that stores the photoresist liquid in the photoresist storage container in an appropriate state, and a blank mask Production method.

A high-sensitivity photoresist liquid is used for the formation and processing of a semiconductor device such as a flat panel display (FPD: Flat Panel Display) or a fine structure such as a magnetic disk or an optical disk. In addition, the application of the photoresist to the blank mask in the mask process is performed by spin coating. The spin coating method is to set the target substrate on the spin coater, and the nozzle is sprayed at a high speed after the photoresist is dropped from the nozzle of the photoresist coating device to the surface of the photoresist coating device, thereby diffusing and coating the photoresist liquid. .

If the photoresist is in a static state, a gel-like insoluble matter may be generated. When the photoresist solution in which the gelled insoluble matter is produced is diffused and coated, the gelled insoluble matter adheres to the surface of the substrate to become a foreign matter, and the photoresist which is the basis of the fine structure is formed. The pattern creates defects. In order to suppress the generation of gelatinous insoluble matter, cyclic filtration of a photoresist liquid is effective. There is known a photoresist liquid supply device in which a circulation filter device is arranged to circulate a photoresist liquid in a bottle-shaped photoresist liquid storage container formed of glass or the like (for example, see JP-A-2014-63807 Bulletin (Patent Document 1)).

In the photoresist liquid supply device described in Patent Document 1, when the photoresist liquid in the bottle-shaped storage container is reduced, a space is generated in the upper portion of the storage container. Then, the air entering the space oxidizes the photoresist remaining in the storage container, and there is a problem that the sensitivity changes.

On the other hand, in addition to the shape of the above-mentioned bottle, the shape of the storage container of the photoresist liquid has a plurality of flexible bags which are formed by a film or the like to prevent air from infiltrating (for example, see International Publication No. 1989/07575 (Patent Literature 2)). Further, a device has been disclosed in which a tube is inserted into a bag-shaped storage container, a photoresist is introduced from the outside of the container, and a photoresist is discharged from the container to circulate the photoresist in the storage container. (See, for example, Japanese Laid-Open Patent Publication No. Hei 9-95565 (Patent Document 3)).

Prior technical literature Previous patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2014-63807

Patent Document 2: International Publication No. 1989/07575

Patent Document 3: Japanese Patent Publication No. 9-95565

However, in the device described in the above Patent Document 3, the position of the tip end of the tube inserted into the container is fixed. Therefore, the photoresist liquid is always introduced into the container from the same position, and in addition, the photoresist liquid in the container is always discharged from the same position. Therefore, the photoresist liquid near the front end of the tube can be stirred by the movement, but the photoresist liquid leaving the front end of the tube does not move and stays. That is, the portion which leaves the front end of the tube cannot sufficiently agitate the photoresist, and the gelation of the photoresist is caused by the dark reaction, which is a problem.

Further, since the apparatus described in Patent Document 3 has one tube, the photoresist liquid cannot be discharged outside the container when the photoresist liquid is introduced into the container, and the photoresist liquid cannot be introduced into the container when the photoresist liquid is discharged outside the container. . That is, the moving direction of the photoresist in the container is limited to a single direction of the introduction direction or the discharge direction, and the photoresist cannot be stirred efficiently, and gelation of the photoresist occurs.

The present invention has been made to solve such problems, and an object of the invention is to provide a photo-resistive liquid which can efficiently circulate a photoresist solution in a container in a storage container having a flexible photoresist liquid. A container, a photoresist supply device, a photoresist liquid coating device, and a photoresist liquid storage device. Further, it is an object of the present invention to provide a method of manufacturing a blank mask.

In order to solve the above problems, for example, the configuration described in the scope of the patent application is employed. The photoresist storage container related to the present invention is a photoresist liquid used for storing photolithography; and has a flexible bag portion having a storage portion for storing a photoresist liquid; and an injection tube connected to the housing portion. The photoresist is injected into the accommodating portion; and the discharge pipe is connected to the accommodating portion, and the photoresist liquid stored in the accommodating portion is discharged outside the photoresist storage container.

Further, the photoresist liquid supply device according to the present invention has a photoresist storage container (having a flexible bag portion, a storage portion for storing a photoresist liquid used for lithography, and an injection tube for connecting In the accommodating portion, the photoresist is injected into the accommodating portion; and the discharge tube is connected to the accommodating portion, and the photoresist liquid stored in the accommodating portion is discharged outside the photoresist storage container); the liquid tank is filled with The temperature adjusting liquid is used to impregnate the photoresist liquid storage container; the temperature regulating liquid circulation mechanism is to circulate the temperature regulating liquid filled in the liquid tank; the temperature control mechanism controls the temperature of the filled temperature adjusting liquid; The mechanism supplies the photoresist liquid in the photoresist storage container to the photoresist liquid application device.

Further, the photoresist liquid-coating apparatus according to the present invention has a photoresist storage container (having a flexible bag portion, a housing portion for storing a photoresist liquid used for lithography, and an injection tube; Connected to the accommodating portion, the photoresist is injected into the accommodating portion; and the discharge tube is connected to the accommodating portion, and the photoresist liquid stored in the accommodating portion is discharged outside the photoresist storage container); the liquid tank is filled with The temperature adjusting liquid is used to impregnate the photoresist liquid storage container; the temperature regulating liquid circulating mechanism is to circulate the temperature regulating liquid filled in the liquid tank; the temperature control mechanism controls the temperature of the filled temperature adjusting liquid; The mechanism supplies the photoresist liquid in the photoresist storage container to the photoresist liquid application device; and the dropping nozzle causes the photoresist supplied from the supply mechanism to drop down to the surface of the substrate.

Further, the photo-resistance liquid storage device of the present invention has a photoresist storage container (having a flexible bag portion, a storage portion for storing a photoresist liquid used for lithography, and an injection tube connected to each other) The accommodating portion injects the photoresist liquid into the accommodating portion; and the discharge tube communicates with the accommodating portion to discharge the photoresist liquid stored in the accommodating portion outside the photoresist liquid storage container; the liquid tank is filled with the liquid The warm liquid is used to impregnate the photoresist storage container; the temperature adjustment liquid circulation mechanism is to circulate the temperature adjustment liquid filled in the liquid tank; and the temperature control mechanism controls the temperature of the filled temperature adjustment liquid.

Further, a method of manufacturing a blank mask according to the present invention has a process of forming a film for pattern formation on one surface of a substrate, and a process of applying a photoresist liquid to the surface of the film and fixing it using a photoresist liquid coating device. ; has the following steps:

a step of generating a circulation by using a discharge pipe and an injection pipe to form a photoresist in the photoresist liquid storage container for storing the photoresist; and circulating the temperature adjustment liquid in the bath of the immersion photoresist storage container; The temperature of the temperature regulating liquid is controlled at a temperature suitable for the temperature of the photoresist coating; and the step of supplying the photoresist suitable for the temperature of the coating to the photoresist coating device.

According to the photoresist storage container according to the present invention, the photoresist liquid stored in the container can be efficiently circulated, and gelation of the photoresist can be suppressed. Further, according to the photoresist liquid storage container according to the present invention, even when the photoresist liquid having a capacity lower than the capacity of the photoresist storage container is stored, it is possible to prevent air or the like from entering the container, and it is also possible to effectively suppress the composition of the photoresist. Sensitivity changes caused by dark reactions with oxygen and the like.

Further, according to the photoresist liquid supply device of the present invention, the photoresist can be supplied to the photoresist liquid application device or the like while suppressing gelation of the photoresist liquid stored in the photoresist storage container. Further, according to the photoresist liquid supply device of the present invention, since air does not enter the photoresist storage container in place of the supplied photoresist liquid, the dark reaction accompanying the composition of the photoresist and oxygen can be effectively suppressed. The sensitivity of the photoresist changes.

Further, according to the photoresist liquid coating apparatus of the present invention, the photoresist can be applied to the substrate or the like while suppressing gelation of the photoresist liquid stored in the photoresist storage container. Therefore, according to the photoresist liquid-coating apparatus according to the present invention, since the insoluble matter is not generated by the gelation, the insoluble matter is not discharged onto the substrate, and a photoresist layer having less foreign matter can be formed. Further, according to the coating apparatus, since the air does not enter the photoresist storage container, the dark reaction between the photoresist and oxygen can be suppressed. Therefore, since the photoresist liquid-coating apparatus according to the present invention can always supply a photoresist liquid excellent in sensitivity stability to the substrate, the formed photoresist layer does not exhibit sensitivity difference on each of the individual substrates.

Further, according to the photoresist liquid storage device of the present invention, the photoresist can be stored in a state in which gelation of the photoresist liquid stored in the photoresist storage container is suppressed. It can prevent air from entering between the photoresist and the storage container, and can effectively suppress the change in the sensitivity of the photoresist accompanying the dark reaction.

Further, according to the method of manufacturing a blank mask according to the present invention, since a blank mask can be produced by using a photoresist which suppresses gelation, a photoresist layer having less foreign matter defects due to gelation insoluble matter can be produced. Blank mask. Further, according to the method, since the contact between the photoresist and the air (oxygen) can be prevented, a blank mask having a photoresist layer having a small variation in sensitivity of each of the individual sheets can be manufactured.

1,11,11’,21‧‧‧Solution liquid storage container

2‧‧‧ bag department

2a‧‧‧Receiving Department

3‧‧‧ ring member

4‧‧‧Retaining components

8‧‧‧Draining tube

9‧‧‧Injection tube

80‧‧‧Photoresist supply device (photoresist storage device)

90‧‧‧Photoresist coating device

40‧‧‧Temperature fluid circulation mechanism

50‧‧‧ Temperature control mechanism

100‧‧‧ Blank mask

Fig. 1 is a schematic longitudinal cross-sectional view showing a photoresist storage container according to a first embodiment of the present invention.

Fig. 2 is a front view of a holding member according to a first embodiment of the present invention.

Fig. 3 is a schematic longitudinal cross-sectional view showing a photoresist storage container according to a second embodiment of the present invention.

Fig. 4 is an explanatory view for explaining the flow of the photoresist liquid in the accommodating portion of the photoresist liquid storage container.

FIG. 5 is an explanatory view for explaining the flow of the photoresist liquid in the accommodating portion of the photoresist liquid storage container according to the second embodiment of the present invention.

Fig. 6 is a schematic longitudinal cross-sectional view showing a photoresist storage container according to a third embodiment of the present invention.

Fig. 7 is a cross-sectional view showing an injection pipe and a discharge pipe according to a third embodiment of the present invention.

FIG. 8 is an explanatory view for explaining the flow of the photoresist liquid in the accommodating portion of the photoresist liquid storage container according to the third embodiment of the present invention.

Fig. 9 is a schematic view showing the configuration of a photoresist liquid storage device, a photoresist liquid supply device, and a photoresist liquid application device according to the present invention.

Fig. 10 is a view showing the results of the sensitivity change test conducted by using a photoresist storage container (using a flexible bag portion).

Figure 11 is a flow chart showing the process of the blank mask manufacturing method of the present invention.

Figure 12A is a schematic cross-sectional view showing one of the processes for fabricating a phase transfer mask.

Figure 12B is a schematic cross-sectional view showing one of the processes for fabricating a phase transfer mask.

Figure 12C is a schematic cross-sectional view showing one of the processes for fabricating a phase transfer mask.

Figure 12D is a schematic cross-sectional view showing one of the processes for fabricating a phase transfer mask.

Figure 12E is a schematic cross-sectional view showing one of the processes for fabricating a phase transfer mask.

Figure 12F is a schematic cross-sectional view showing one of the processes for fabricating a phase transfer mask.

Hereinafter, the form for carrying out the invention will be described with reference to the drawings.

[First Embodiment of Photoreceptor Storage Container]

1 is a schematic longitudinal cross-sectional view of a photoresist storage container 1 according to a first embodiment of the present invention, and FIG. 2 is a front view of a holding member 4 according to a first embodiment of the present invention.

<All composition>

The photoresist storage container 1 according to the present embodiment includes a bag portion 2 having a storage portion 2a for storing a photoresist liquid, and a ring member 3 provided in the bag portion 2 and having an opening portion 3a communicating with the housing portion 2a. And the holding member 4 and the ring member 3 are fitted.

<bag department>

The bag portion 2 forms a housing portion 2a for storing the photoresist liquid internally by heat-sealing the four sides of the film in such a manner as to overlap each other. The pocket portion 2 is formed in a rectangular flat shape. Further, the corner portion of the accommodating portion 2a is formed in an arc shape so that the photoresist liquid does not easily remain in the corner portion. Further, in the present embodiment, although the films are opposed to each other and the four sides are heat-sealed, the present invention is not limited thereto. Further, a chamfer may be formed at the bottom of the film. Further, in order to increase the efficiency of use of the photoresist, the bottom edge of the bag may be formed into a convex curved shape or a tapered shape toward the bottom direction.

As the material of the film, for example, a hydrocarbon-based polymer sheet such as polyethylene or polypropylene can be used. A multilayer film can be used in addition to a single layer film in terms of the construction of the film. For example, a highly airtight film or a functional film having a light blocking property for blocking a gas such as oxygen or water vapor may be separately provided.

<ring member>

The ring-shaped member 3 as the engagement holding portion is a cylindrical member having an opening 3a (which communicates with the accommodating portion 2a of the bag portion 2). The opening portion 3a of the ring member 3 is engaged with the engaging portion 4b of the holding member 4 when the ring member 3 is fitted to the holding member 4. The ring member 3 is thermally welded to the film at the upper portion of the bag portion 2 as shown in FIG.

The ring member 3 is preferably manufactured by an injection molding method. The resin to be used is not particularly limited as long as it can be injection-molded. However, it is usually a high-density polyethylene which is rigid at a high temperature and is not easily embrittled at a low temperature.

<holding member>

The holding member 4 is formed by the head portion 4a (outer than the bag portion 2 when the ring mouth member 3 is fitted) and the engaging portion 4b (inserted into the opening portion 3a of the ring mouth member 3, the front end of which is located in the pocket portion 2 containment Part 2a). As shown in FIG. 1, the opening 3a of the ring member 3 is engaged with the engaging portion 4b of the holding member 4, and the holding member 4 is fitted to the ring member 3.

As shown in Fig. 2, the head portion 4a of the holding member 4 is formed in a cylindrical shape, and a discharge pipe hole 8a for inserting the discharge pipe 8 is formed in the vicinity of the center of the upper surface 4c of the head portion 4a. The discharge pipe hole 8a is formed to penetrate the holding member 4 in the axial direction. Further, the diameter of the discharge pipe hole 8a is formed to be slightly smaller than the outer diameter of the discharge pipe 8. Thereby, the discharge pipe 8 inserted into the discharge pipe hole 8a can be held at a predetermined position, and even if the discharge pipe 8 is attached to the holding member 4, the inside of the photoresist liquid storage container 1 can be kept in a liquid-tight state.

An injection pipe hole 9a for inserting the injection pipe 9 is formed in the side peripheral surface 4d of the head portion 4a of the holding member 4. The injection pipe hole 9a is formed to extend in a direction perpendicular to the axial direction of the holding member 4. Further, the aperture of the injection tube hole 9a is formed to be slightly smaller than the outer diameter of the injection tube 9. Thereby, the injection pipe 9 inserted into the injection pipe hole 9a can be held at a predetermined position, and even if the injection pipe 9 is attached to the holding member 4, the inside of the photoresist storage container 1 can be kept in a liquid-tight state.

The engaging portion 4b of the holding member 4 is connected to the lower portion of the head portion 4a, and is formed in a cylindrical shape having a diameter slightly smaller than the diameter of the head portion 4a. The outer diameter of the engaging portion 4b is formed to be slightly larger than the diameter of the opening portion 3a of the ring-shaped member 3. Thereby, when the holding member 4 and the ring member 3 are fitted, the inside of the photoresist storage container 1 can be liquid-tightly held. Further, an O-ring may be disposed between the engaging portion 4b and the ring member 3 to improve liquid tightness. Further, a step 4e is formed between the head portion 4a of the holding member 4 and the engaging portion 4b. By causing the step 4e to be fastened to the edge of the opening portion 3a of the ring-shaped member 3, when the holding member 4 and the ring-shaped member 3 are fitted, the holding member 4 can be prevented from being pressed into the ring more than necessary. Port member 3.

A cylindrical space portion 5 is formed inside the holding member 4. The lower portion of the space portion 5 communicates with the accommodating portion 2a, and the upper portion of the space portion 5 communicates with the discharge tube hole 8a and the injection tube hole 9a. Further, the diameter of the space portion 5 is formed to be larger than the outer diameter of the discharge pipe 8. Thereby, even if the discharge pipe 8 is attached to the holding member 4, the gap of the flowing photoresist can be ensured between the discharge pipe 8 and the inner wall of the holding member 4.

The holding member 4 is preferably manufactured by injection molding. The resin to be used is not particularly limited as long as it is a resin that can be injection-molded, and is generally preferably a high-density polyethylene which is rigid even at a high temperature and is not easily embrittled at a low temperature.

As shown in Fig. 1, the discharge pipe 8a formed in the upper surface 4c of the head portion 4a of the holding member 4 is inserted into the discharge pipe 8 in the axial direction of the holding member 4. The discharge pipe 8 is formed of a thin pipe, and a tapered surface portion 8b is formed at an end portion of the discharge pipe 8. By forming the tapered surface portion 8b at the distal end, even if the front end of the discharge tube 8 is located near the bottom of the bag portion 2, the photoresist liquid remaining in the vicinity of the bottom portion of the accommodating portion 2a can be discharged. The other end of the discharge pipe 8 is connected to a pump 31 which will be described later.

The injection pipe hole 9a formed in the side peripheral surface 4d of the holding member 4 is inserted into the injection pipe 9 in a direction perpendicular to the axial direction of the holding member 4. The injection pipe 9 is composed of a thin pipe, and is disposed such that the front end of the injection pipe 9 is located on the front side of the space portion 5. That is, the injection pipe 9 is not in contact with the discharge pipe 8 provided in the space portion 5, but is communicated with the space portion 5 of the holding member, that is, between the discharge pipe 8 and the inner wall of the holding member 4. The space formed. The other end of the injection pipe 9 is connected to a pump 31 to be described later.

In the present embodiment, the insertion direction of the discharge pipe 8 attached to the holding member 4 and the insertion direction of the injection pipe 9 are different, and the discharge pipe 8 and the injection pipe 9 do not need to have a double pipe structure. Thereby, the structure of the photoresist liquid storage container 1 can be simplified.

The material of the discharge pipe 8 and the injection pipe 9 is usually a high-density polyethylene which is rigid even at a high temperature and is not easily embrittled at a low temperature. Further, the tapered surface portion 8b is formed by obliquely cutting the front end of the discharge pipe 8.

Further, an inclined portion may be formed on the upper surface 4c of the head portion 4a of the holding member 4. Thereby, when the work of fitting the holding member 4 and the ring mouth member 3 is performed by means of a lever or the like, one part of the instrument can be released to the space portion formed above the inclined portion.

<Assembly of Photoreceptor Storage Container>

First, in a state where the holding member 4 is removed from the ring mouth member 3, the photoresist liquid is injected from the opening portion 3a of the ring mouth member 3, and the photoresist liquid is stored in the housing portion 2a of the bag portion 2. When the photoresist storage container 1 is not used immediately, the opening 3a of the ring member 3 is stored in a state of being plugged. In addition to the usual photoresist solution, the injected photoresist can also be used with high-sensitivity photoresist, especially chemically amplified photoresist. The photoresist liquid storage container 1 of the present embodiment does not enter the air due to the presence of air. The flexible bag portion 2 in the container portion 2a can also store a chemically amplified resist liquid which is easily oxidized by air.

When the container 1 is stored in the photoresist, the plug of the opening 3a is removed, and the holding member 4 to which the discharge pipe 8 and the injection pipe 9 are attached is fitted to the ring member 3. At this time, the front end of the discharge pipe 8 is inserted into the accommodating portion 2a from the opening 3a, and then the engaging portion 4b of the holding member 4 is engaged with the opening portion 3a of the ring member 3 to form the photoresist liquid storage container 1 . At this time, the discharge pipe 8 is attached to the holding member 4 such that the front end of the discharge pipe 8 is located near the bottom of the bag portion 2. Further, one portion of the discharge pipe 8 may be bent to be engaged with the edge of the discharge pipe hole 8a of the holding member 4 to define the position of the front end of the discharge pipe 8 of the accommodating portion 2a. Thereby, it is possible to prevent the residual of the photoresist liquid in the accommodating portion 2a caused by the damage of the bag portion 2 caused by the deep insertion into the discharge tube 8 or the shallow insertion into the front end of the discharge tube 8.

As shown in FIG. 1, the assembled photoresist liquid storage container 1 is placed in a photoresist liquid supply device, a photoresist liquid application device, and a photoresist liquid storage device, which will be described later.

When the photoresist liquid stored in the accommodating portion 2a is circulated, the photoresist liquid is discharged from the front end of the injection tube 9. The photoresist discharged from the front end of the injection tube 9 is moved to the housing portion 2a of the bag portion 2 through the space portion 5 formed by the holding member 4. Then, the front end of the discharge pipe 8 is sucked into the discharge pipe 8 and discharged to the outside of the photoresist liquid storage container 1. In this manner, the photoresist liquid stored in the accommodating portion 2a is agitated with the movement of the photoresist liquid discharged from the injection tube 9 and discharged from the discharge tube 8 to the storage container 1. By using the photoresist liquid storage container 1 of the present embodiment, since the photoresist liquid does not remain in the accommodating portion 2a, gelation of the photoresist liquid due to the dark reaction can be suppressed.

[Second Embodiment of Photoreceptor Storage Container]

Next, the photoresist liquid storage container 11 according to the second embodiment of the present invention will be described. The arrangement of the photoresist liquid storage container 11 of the present embodiment in the discharge pipe 8 and the injection pipe 9 of the holding member 4 is different from that of the first embodiment. The configuration of the whole of the photo-resistance storage container 11 of the present embodiment is the same as that of the first embodiment, and the description of the same reference numerals will be given to the parts in FIG.

Fig. 3 is a schematic longitudinal cross-sectional view showing a photoresist storage container 11 according to a second embodiment of the present invention. 4 and 5 are explanatory views for explaining the flow of the photoresist liquid in the accommodating portion 2a of the photoresist liquid storage container 11.

As shown in FIG. 3, in the holding member 4, the discharge pipe 8 and the injection pipe 9 are attached in parallel in the axial direction of the holding member 4. The discharge pipe 8 attached to the holding member 4 and the front end of the injection pipe 9 are disposed so as to be positioned inside the accommodating portion 2a. The discharge pipe hole 8a and the injection pipe hole 9a are formed in the upper surface 4c of the head portion 4a of the holding member 4 of the present embodiment, and the discharge pipe hole 8a and the injection pipe hole 9a are formed so as to penetrate the holding member 4 in the axial direction.

The difference from the above-described first embodiment is that in the present embodiment, the front end of the injection pipe 9 is also disposed so as to be positioned inside the accommodating portion 2a. Specifically, the front end of the injection pipe 9 is disposed so as to be in the vicinity of the opening portion 3a of the ring-shaped member 3. Similarly to the first embodiment, the position of the front end of the discharge pipe 8 inserted into the accommodating portion 2a is disposed so as to be located near the bottom of the accommodating portion 2a. Therefore, the position of the front end of the injection pipe 9 inserted into the accommodating portion 2a is disposed above the position of the front end of the discharge pipe 8 and is disposed above.

In the present embodiment, in the accommodating portion 2a, the position of the front end of the injection pipe 9 is upward, so that the position of the front end of the discharge pipe 8 is separated from the position of the front end of the injection pipe 9 in the vertical direction. Thereby, the moving distance from the photoresist liquid injected from the front end of the injection pipe 9 to the front end of the discharge pipe 8 becomes long, and the photoresist liquid in the accommodating portion 2a can be surely stirred. Further, when the position of the front end of the injection pipe 9 is located above, the movement of the photoresist liquid injected from the injection pipe 9 can be smoothly performed by gravity, and the photoresist liquid in the accommodating portion 2a can be surely stirred.

In the present embodiment, when the photoresist liquid stored in the accommodating portion 2a is circulated, the photoresist liquid is directly injected into the accommodating portion 2a of the bag portion 2 from the front end of the injection tube 9, and the front end of the discharge tube 8 is The photoresist is discharged to the outside of the container 11. In the present embodiment, the photoresist liquid in the accommodating portion 2a is agitated by the movement of the photoresist liquid, and gelation of the photoresist liquid due to the dark reaction can be suppressed.

Fig. 4 is a view showing an embodiment in which the discharge pipe 8 and the position of the front end of the injection pipe 9 are disposed at the same height in the accommodating portion 2a. In the photoresist storage container 11' of this embodiment, the discharge pipe 8 and the front end of the injection pipe 9 are disposed near the bottom of the accommodating portion 2a. Further, in the figure, the amount of the photoresist in the accommodating portion 2a is reduced, and the air in the accommodating portion 2a is discharged outside the container to cause the flexible bag portion 2 to atrophy, and the photoresist can be moved in the accommodating portion 2a. A state in which space is reduced. When the photoresist When the movable space is small, the photoresist liquid near the front end of the discharge pipe 8 is isolated from the photoresist liquid near the front end of the injection pipe 9, and a so-called effusion Q is generated inside the accommodating portion 2a. If the effusion Q is generated in this manner, the photoresist liquid in the accommodating portion 2a cannot be circulated.

Fig. 5 is a view for explaining the circulation of the photoresist liquid in the case where the residual amount of the photoresist in the accommodating portion 2a is reduced in the resist liquid storage container 11 shown in Fig. 3 .

As shown in Fig. 5, since the space in which the resist liquid can move due to the shrinkage of the flexible bag portion 2 is reduced, the liquid accumulation Q is generated in the vicinity of the front end of the injection tube 9. However, in the present embodiment, the end of the effusion Q can be guided by the discharge pipe 8 by contact with the outer peripheral surface of the discharge pipe 8, and reaches the front end of the discharge pipe 8 by gravity. The photoresist liquid reaching the front end of the discharge pipe 8 is discharged outside the container 11. By using the photoresist liquid storage container 11 of the present embodiment, even if the photoresist liquid in the accommodating portion 2a is reduced to a state in which the liquid accumulation Q is likely to occur, the photoresist liquid in the accommodating portion 2a can be surely made. Loop. Thereby, gelation of the photoresist liquid caused by the dark reaction can be suppressed.

[Third Embodiment of Photoreceptor Storage Container]

Next, the photoresist storage container 21 according to the third embodiment of the present invention will be described. The arrangement of the discharge liquid storage container 21 of the present embodiment in the discharge pipe 8 and the injection pipe 9 provided in the holding member 4 is different from that of the first embodiment, and has a double pipe structure. The entire configuration of the photoresist liquid storage container 21 of the present embodiment is omitted as described in the first embodiment, and the same reference numerals are given to the portions in FIG.

Fig. 6 is a schematic longitudinal cross-sectional view showing a photoresist storage container 21 according to a third embodiment of the present invention. Fig. 7 is a cross-sectional view showing the discharge pipe 8 and the injection pipe 9 shown in line A-A of Fig. 6, and Fig. 8 is an explanatory view for explaining the flow of the photoresist liquid in the accommodating portion 2a of the photoresist liquid storage container 21.

As shown in Fig. 6, the photoresist storage container 21 of the present embodiment has a so-called double tube structure in which the diameter of the injection tube 9 is larger than the diameter of the discharge tube 8, and the discharge tube 8 is disposed inside the injection tube 9. The discharge pipe 8 and the injection pipe 9 forming the double pipe structure are inserted into the through holes 9b formed in the upper surface 4c of the head portion 4a of the holding member 4. The through hole 9b is formed to have a diameter slightly smaller than the outer diameter of the injection pipe 9, and is formed to penetrate the holding member 4 in the axial direction.

As shown in Fig. 7, the discharge pipe 8 having the double pipe structure and the injection pipe 9 have a common concentric shaft, and a space portion 10 is formed between the outer circumferential surface of the discharge pipe 8 and the inner circumferential surface of the injection pipe 9 to allow The photoresist liquid injected from the injection tube 9 passes.

Further, the position of the front end of the discharge pipe 8 inserted into the accommodating portion 2a is disposed so as to be located near the bottom of the accommodating portion 2a, and the position of the front end of the injection pipe 9 inserted into the accommodating portion 2a is compared with the front end of the discharge pipe 8. The way the location is above is configured. Specifically, the front end of the injection pipe 9 is disposed so as to protrude from the opening portion 3a of the ring member 3 and to be positioned in the accommodating portion 2a. Further, the position of the front end of the injection pipe 9 may be in the through hole 9b of the holding member 4.

Fig. 8 is a view for explaining the circulation of the photoresist in the case where the residual amount of the photoresist in the accommodating portion 2a is reduced in the resist liquid storage container 1 shown in Fig. 6.

As shown in FIG. 8, when the residual amount of the photoresist in the accommodating portion 2a is small, the photoresist liquid injected from the front end of the injection tube 9 is along the discharge tube 8 disposed inside the double tube structure. The outer peripheral surface reaches the vicinity of the front end of the discharge pipe 8. That is, no liquid is generated near the front end of the injection tube 9. The photoresist liquid that has reached the front end of the discharge pipe 8 is discharged outside the storage container 21 by the discharge pipe 8. In the photoresist liquid storage container 21 of the present embodiment, even if the amount of photoresist remaining in the accommodating portion 2a is small, the liquid accommodating portion 2a is likely to be in a state in which liquid accumulation is likely to occur, and the vicinity of the front end of the injection tube 9 is not The liquid is generated, and the photoresist can be circulated in the accommodating portion 2a. Thereby, gelation of the photoresist liquid caused by the dark reaction can be suppressed.

As described above, the photoresist storage container of the present invention has a flexible bag portion 2 composed of a film, regardless of the embodiment.

In the following, a comparison was made between the photoresist storage container using the flexible bag portion and the photoresist storage container using the non-flexible bottle as the bag portion by the sensitivity change test.

<sensitivity change test> [Example 1]

A resist liquid storage container is produced by using a bag portion made of a film and having flexibility.

[Comparative Example 1]

The bag portion is made of a glass bottle which is not flexible, and a photoresist liquid storage container is produced.

The photoresist storage container prepared above was stored in an environment at a temperature of 10 degrees, and the test was performed one week later, two weeks later, one month later, two months later, and three months later from the start of storage. Conduct an evaluation.

In the evaluation, the photoresist layer stored in the photoresist storage container was used to form a photoresist layer on the substrate, and the CDU (Critical Dimension Uniformity) was measured to evaluate the sensitivity. The result is shown in FIG.

In addition, in the photoresist layer used for the evaluation, a chemically amplified positive photoresist (PRL009S manufactured by Fujifilm Electronic Materials Co., Ltd.) was used for the photoresist, and pre-exposure baking was performed: 190 degrees, 60 seconds, film thickness, and film thickness: 120 nm. Conditions are formed.

As is apparent from Fig. 10, the photoresist storage container of the first embodiment can maintain the value of the CDU in a higher state than the photoresist storage container of the comparative example 1. As described above, by using the flexible bag portion as in the photoresist liquid storage container of the present embodiment, it is possible to prevent the photoresist liquid during storage from coming into contact with the air, and it is possible to reduce the deterioration of the sensitivity of the photoresist liquid over time.

As described above, in any of the embodiments, the photoresist liquid storage container according to the present invention causes the photoresist liquid stored in the accommodating portion 2a to be circulated.

Hereinafter, a comparison is made between the photoresist liquid storage container that causes the photoresist liquid stored in the housing portion to circulate, and the photoresist liquid storage container that does not cause the photoresist liquid stored in the housing portion to circulate by the foreign matter test.

<foreign object test> [Example 2]

The photoresist storage container having the bag portion formed of the film is used for a photoresist liquid supply device to be described later, and is stored for 24 hours while performing circulation filtration.

[Comparative Example 2]

The photoresist storage container having the bag portion formed of the film was used for the photoresist liquid supply device, and was stored without being circulated for 24 hours.

After that, a photoresist layer was deposited on the substrate using a photoresist liquid stored in a resist liquid storage container, and the number of defects of the photoresist layer caused by gelation of the photoresist liquid was counted, and evaluation was performed five times. . The conditions for forming the photoresist layer are the same as those for the sensitivity change test over time.

Further, in the case of Comparative Example 2, a filter was provided in the discharge pipe.

As a result, in the case of Example 2, all the defects were not counted to have a depth of 0.2 μm or more, but in the case of Comparative Example 2, the defect having a depth of 0.2 μm or more was counted on the average of 11 portions.

From the results, it was found that in the case of Example 2, gel-like foreign matter did not appear in the photoresist liquid in the accommodating portion as compared with the case of Comparative Example 2. Further, as is clear from the results of Comparative Example 2, even if a filter was used, the gel-like foreign matter generated in the photoresist liquid could not be completely removed. According to the photoresist liquid storage container of the present embodiment, the circulation of the photoresist liquid stored in the container can suppress the gelation of the photoresist solution caused by the dark reaction, and the storage of the photoresist in the photoresist can be suppressed. Gelatinous foreign matter is produced.

[Embodiment of photoresist liquid supply device, photoresist liquid application device, and photoresist liquid storage device]

Hereinafter, embodiments of the photoresist liquid supply device, the photoresist liquid application device, and the photoresist liquid storage device using the photoresist liquid storage container 1 according to the present invention will be described with reference to the drawings.

Fig. 9 is a schematic view showing the configuration of a photoresist liquid supply device 80, a photoresist liquid application device 90, and a photoresist liquid storage device according to the present invention. Further, in Fig. 9, the present system of the photoresist liquid supply device 80 is shown in a partially broken partial cross-sectional view, and the configuration of the fluid control system is shown in a fluid circuit diagram. Further, the photoresist liquid application device 90 is provided with a drip nozzle 20 for dropping a photoresist liquid on the surface of the target substrate S such as a blank mask provided on the spin coater 41.

The photoresist liquid supply device 80 includes a photoresist liquid storage container 1 that stores a liquid photoresist liquid, and a liquid tank 12 that is immersed in the photoresist liquid storage container 1 that is filled therein by the temperature control liquid 14 that is filled therein. . In addition, the photoresist liquid storage container 1 may be housed in the photoresist liquid supply device 80 in a state in which it is housed in a cylindrical outer container.

The inner wall of the internal space of the division liquid tank 12 has a cylindrical shape, and the photoresist liquid storage container 1 is accommodated in the internal space. By forming the inner wall of the liquid tank 12 into a cylindrical shape, even when the rectangular photoresist storage container 1 is housed, the flow around the temperature control liquid 14 can be formed or promoted. Further, although not shown, a liquid amount window for visually measuring the photoresist liquid in the resist liquid storage container 1 may be provided in one portion of the liquid tank 12.

The liquid tank 12 is formed in a liquid-tight manner so that the temperature-control liquid 14 can be filled to a certain height. Further, the liquid tank 12 is provided with an upper cover 18 that can be fitted into the holding member 4 of the photoresist liquid storage container 1 to prevent splashing of the temperature control liquid 14. In this case, even if the photoresist liquid stored in the accommodating portion 2a is small, the resist liquid storage container 1 is attached to the upper cover 18 in a state where the bag portion 2 does not float. Although pure water can be used for the temperature control liquid 14, it is also possible to add a vaporization inhibitor such as ethylene glycol to pure water as a water liquid for the purpose of stabilization of the liquid amount.

The temperature control liquid 14 is supplied into the liquid tank 12 via the water supply line 16 in advance. Further, the tempering liquid 14 filled in the liquid tank 12 can be drained via the drain line 17. In the liquid tank 12, the temperature adjustment liquid 14 is filled to a higher water level than the photoresist liquid level of the photoresist liquid storage container 1 disposed at a predetermined position, whereby the photoresist liquid storage container 1 is subjected to the temperature adjustment liquid 14 Impregnation.

The photoresist liquid supply device 80 is provided with a photoresist liquid supply mechanism 30 for supplying the photoresist liquid in the photoresist liquid storage container 1 to the photoresist liquid application device 90. The resist liquid supply mechanism 30 has at least a pump 31 for supplying a photoresist liquid, and a main body discharge pipe 32 connected between the resist liquid storage container 1 and the suction side of the pump 31, and a negative pressure generated by the pump 31. The photoresist liquid in the light-absorptive liquid storage container 1 is placed in the upper portion, and the supply tube 33 is connected to the discharge side of the pump 31, and the photoresist liquid discharged from the pump 31 is supplied to the photoresist liquid application device 90 (the dropping nozzle 20). ). The front end of the main body discharge pipe 32 is connected to the discharge pipe 8 to which the photoresist storage container 1 is attached. Further, the discharge pipe 8 may directly mount the main body discharge pipe 32 to the holding member 4 of the photoresist liquid storage container 1.

The pump 31 is preferably a rotary pump in which the discharge flow rate of the photoresist liquid is constant and the occurrence of voids (bubbles) is extremely small. In addition, the filter 34 for filtering and removing particles or gelation components which may be contained in the photoresist may be provided in the discharge side pipe of the pump 31 as shown in Fig. 9 . Further, although not shown, such a filter may be provided in the suction side pipe of the pump 31. Further, such a filter may be provided in the middle of a pipe through which the photoresist liquid circulation mechanism 70 circulates the photoresist liquid.

The liquid tank 12 is provided with a temperature adjustment liquid circulation mechanism 40 that circulates the temperature adjustment liquid 14 in the liquid tank 12, and a temperature control mechanism 50 that adjusts the temperature adjustment liquid 14 in the liquid tank 12 to an appropriate temperature. The temperature adjustment liquid circulation mechanism 40 and the temperature control mechanism 50 can maintain the temperature adjustment liquid 14 in a constant state, thereby avoiding a local temperature difference in the photoresist liquid in the photoresist liquid storage container 1.

Further, the photoresist liquid supply device 80 is provided with a photo-resistance circulation mechanism 70 for circulating the photoresist in the photoresist storage container 1. In FIG. 9, the photoresist liquid circulation mechanism 70 is configured to include a pump 31, a main body discharge pipe 32 connected to the suction port of the pump 31, a suction port side inserted into the photoresist liquid storage container 1, and a return pipe 36. The supply pipe 33 connected to the discharge port of the pump 31 is branched by the three-way valve 35, and the injection port side is inserted into the resist liquid storage container 1. A degasser 42 is provided in the return pipe 36 for deaerating the air accumulated inside the body discharge pipe 32 and the return pipe 36 toward the outside. The front end of the return pipe 36 is connected to the injection pipe 9 installed in the photoresist liquid storage container 1. Further, the return pipe 36 may be directly attached to the holding member 4 of the resist liquid storage container 1 in terms of the injection pipe 9.

The photoresist circulation mechanism 70 is switched to the return pipe 36 side by the communication of the three-way valve 35 to function. When the photoresist liquid is supplied to the photoresist coating device 90, the communication of the three-way valve 35 is switched to the supply pipe 33 side. The three-way valve 35 can also be constructed by a solenoid valve, and is programmed to automatically control the switching of the operation mode of the supply/circulation of such a photoresist. Alternatively, the manual operation type three-way valve 35 can be used to manually perform such switching at any time.

According to the photoresist liquid supply device 80 of the present embodiment, the photoresist liquid stored in the accommodating portion 2a of the resist liquid storage container 1 can be circulated and supplied to the photoresist liquid application device 90 or the like. Therefore, gelation of the photoresist liquid in the photoresist storage container 1 can be suppressed, and the photoresist liquid in a state in which gelled foreign matter is small can be supplied to the photoresist liquid application device 90 or the like. Further, according to the photoresist liquid application device 90 of the present embodiment, the photoresist can be applied to the substrate or the like using a photoresist having no gel-like foreign matter.

The photoresist liquid supply device 80 having the above configuration also functions as a photoresist liquid storage device that stores the photoresist liquid in an appropriate state. In this case, the photoresist liquid storage device includes a photoresist storage container 1 for storing the photoresist liquid, and a liquid bath 12 for immersing the photoresist liquid storage container 1 with the temperature adjustment liquid 14, so that the temperature adjustment liquid 14 is circulated. The warm liquid circulation mechanism 40 and the temperature control mechanism 50 that controls the temperature of the temperature control liquid 14.

According to this photoresist liquid storage device, the temperature of the temperature control liquid 14 is controlled by the temperature control means 50, so that the temperature of the photoresist liquid stored in the photoresist liquid storage container 1 can be made appropriate. The temperature range of the temperature control liquid 14 controlled by the temperature control mechanism 50 is at least comprised of a first temperature suitable for coating of the photoresist (for example, a room temperature of 23 ° C) and a second temperature suitable for storage of the photoresist (for example) 10 ° C cold temperature is preferred.

Thereby, the photoresist can be maintained at the second temperature (cold temperature) during the period in which the coating is not applied. For example, when a chemically amplified photoresist having a large change in sensitivity at room temperature is used, the accumulation time of the photoresist placed in a room temperature environment can be reduced, and the sensitivity of the photoresist can be suppressed from deteriorating. Further, according to the photoresist liquid storage device of the present embodiment, the photoresist liquid stored in the housing portion 2a of the resist liquid storage container 1 can be stored in a circulating state. Therefore, gelation of the photoresist liquid in the resist liquid storage container 1 can be suppressed, and the photoresist can be stored in a state where the occurrence of gel-like foreign matter is suppressed.

[Embodiment of Manufacturing Method of Blank Mask]

Next, an embodiment of a method of manufacturing a blank mask according to the present invention will be described.

The blank mask is manufactured, for example, in accordance with the process flow shown in FIG.

First, the surface of the blank mask substrate S is polished to obtain a high flatness of a surface roughness of 1 nm or less (step S1). A light shielding film made of a metal thin film such as Cr is formed on the polishing surface of the substrate S (step S2). As the film formation method of the light shielding film, a vacuum deposition method, a sputtering method, or the like can be used.

The photoresist liquid supply device 80 is set before the photoresist coating process is performed by the photoresist coating device 90. As shown in FIG. 9, the photoresist liquid supply device 80 includes a photoresist liquid storage container 1 for storing a photoresist liquid, and a supply mechanism 30 for supplying a photoresist liquid in the photoresist liquid storage container 1 to the dropping nozzle 20 The liquid tank 12 is immersed in the photoresist liquid storage container 1 with the temperature control liquid 14 filled therein; the temperature adjustment liquid circulation mechanism 40 is configured to circulate the temperature adjustment liquid 14; and the temperature control mechanism 50 controls the temperature adjustment liquid 14 temperature.

In preparation for the photoresist supply device 80, the photoresist storage container 1 storing the photoresist is immersed in the liquid tank 12 filled with the temperature control liquid 14. Then, the temperature adjustment liquid circulation mechanism 40 is operated to circulate the temperature adjustment liquid 14 in the liquid tank 12 (step S3).

At the same time, the temperature control mechanism 50 is operated to control the temperature of the temperature regulating liquid 14 circulating in the liquid tank 12 to a temperature suitable for the photoresist coating (for example, a room temperature of 23 ° C) (step S4).

Next, the photoresist liquid is supplied from the photoresist liquid supply device 80 to the photoresist liquid application device 90 by the supply mechanism 30 (step S5). Then, with respect to the blank mask substrate S placed on the spin coater 41, the photoresist liquid is dropped from the dripping nozzle 20 by a predetermined amount. By rotating the spin coater 41 at a high speed, the photoresist liquid is uniformly spread on the surface of the blank mask substrate S (step S6).

Then, the blank mask substrate S coated with the photoresist liquid is moved to the hot plate device, and the surface temperature of the blank mask substrate S is maintained at about 100 ° C to be baked (step S7). Thereby, the organic solvent contained in the photoresist liquid is evaporated, and the photoresist is fixed to the substrate S for the blank mask.

[Examples]

In the present embodiment, a blank mask substrate (translucent substrate) composed of synthetic quartz glass having a main surface of about 152 mm × about 152 mm and a thickness of about 6.25 mm was prepared. This blank mask substrate is obtained by polishing the end surface and the main surface to a predetermined surface roughness, and then applying a predetermined washing treatment and drying treatment.

Next, a halftone phase shift film (film for pattern formation) composed of molybdenum nitride and niobium is formed on the blank mask substrate.

Specifically, a blank mask substrate is provided in a monolithic DC sputtering apparatus, and a mixed target of molybdenum (Mo) and bismuth (Si) (Mo: Si = 10 at%: 90 at%) is used, and argon (Ar) is used. Mixed gas atmosphere with nitrogen (N ₂ ) and helium (He) (gas flow ratio Ar: N ₂ : He = 5:49:46), gas pressure 0.3 Pa, power of DC power source is 3.0 kW, by reactive splash The plating (DC sputtering) forms a MoSiN film composed of molybdenum, niobium, and nitrogen at a film thickness of 69 nm.

Next, the substrate on which the above MoSiN film was formed was subjected to heat treatment as an annealing treatment. Specifically, heat treatment was carried out in a heating furnace at a heating temperature of 450 ° C for 1 hour in the air. In addition, the MoSiN film has a transmittance of 6.16% in an ArF excimer laser and a phase difference of 184.4 degrees.

Next, a light-shielding film (film for pattern formation) made of a chromium-based material is formed on the halftone phase shift film.

Specifically, a chromium (Cr) target is used, and a mixed gas atmosphere of argon (Ar) and carbon dioxide (CO ₂ ) and nitrogen (N ₂ ) and helium (He) (gas flow ratio Ar: CO ₂ : N ₂ : He) =20:35:10:30) A CrOCN film was formed by a reactive sputtering (DC sputtering) at a film thickness of 30 nm at a gas pressure of 0.2 Pa and a DC power of 1.7 kW.

Next, a chromium (Cr) target was used, in a mixed gas atmosphere of argon (Ar) and nitrogen (N ₂ ) (gas flow ratio Ar: N ₂ = 25:75), a gas pressure of 0.1 Pa, and a DC power supply of 1.7 kW. A CrN film was formed by reactive sputtering (DC sputtering) at a film thickness of 4 nm.

Further, a chromium (Cr) target is used in a mixed gas atmosphere of argon (Ar) and carbon dioxide (CO ₂ ) and nitrogen (N ₂ ) and helium (He) (gas flow ratio Ar: CO ₂ : N ₂ : He = 20:35:5:30) A CrOCN film was formed with a film thickness of 14 nm by reactive sputtering (DC sputtering) at a gas pressure of 0.2 Pa and a power of 1.7 kW of a DC power source.

In the above procedure, a chromium-based material light-shielding film (film thickness: 48 nm) having a three-layered structure of a CrOCN film, a CrN film, and a CrOCN film was formed from the substrate side. A halftone phase shift blank mask (blank mask) is obtained by the above process. Further, in the blank mask of the present embodiment, the optical density (OD) with respect to the ArF excimer laser (wavelength: 193 nm) was 3.0, and the surface reflectance of the light-shielding film was 20%.

According to the method for producing a photoresist mask of the present embodiment, since the photoresist liquid in the resist liquid storage container 1 is circulated, gelation of the photoresist liquid caused by the dark reaction is suppressed, and gelled foreign matter is less. The photoresist can be used to create a blank mask with few defects. Further, in the present embodiment, the substrate for the photoresist is used as the substrate for applying the photoresist, but the substrate for imprint may be applied.

<Manufacture of Halftone Phase Shift Mask>

Next, the phase shift mask 150 is fabricated using the blank mask manufactured by the above method. 12A to 12F are schematic cross-sectional views showing a process of manufacturing the phase shift mask 150 using the phase transfer blank mask 100. First, the photoresist film 104 is formed on the blank mask 100 with the photoresist liquid coating device 90 (see FIG. 12A).

Next, the photoresist film 104 formed on the blank mask 100 is patterned by a phase shift pattern by an electron beam drawing device, and then developed with a predetermined developer to form a photoresist pattern 104a (see FIG. 12B).

Then, the light-shielding film 103 (Cr-type light-shielding film) is etched by the photoresist pattern 104a as a mask to form the light-shielding film pattern 103a (see FIG. 12C). A mixed gas of Cl ₂ and O ₂ is used in the dry etching gas.

Next, the phase shift pattern 102a is formed by etching the halftone phase shift film 102 (MoSiN film) using the light shielding film pattern 103a as a mask (see FIG. 12D). A mixed gas of SF ₆ and He is used for the dry etching gas.

Next, the photoresist film 104 is formed in the same manner on the blank mask 100, and after patterning of the light-shielding tape by the electron beam drawing device, the photoresist pattern 104b is formed by development with a predetermined developer (see FIG. 12E).

Next, the light-shielding film pattern 103a (light-shielding film) 103b is formed by etching the light-shielding film pattern 103a (Cr-type light-shielding film) by using the said photoresist pattern 104b as a mask. A mixed gas of Cl ₂ and O ₂ is used in the dry etching gas.

Next, the remaining photoresist pattern is peeled off to obtain a phase shift mask 150 (see Fig. 12F). According to the present embodiment, since the blank mask 100 having few defects is used as described above, a high-quality phase shift mask 150 can be obtained.

The present invention has been described above based on the embodiments, but the present invention is not limited to the configurations described in the above embodiments, and the configuration can be appropriately changed without departing from the scope of the invention. example For the sake of easy understanding of the detailed description of the present invention, the above embodiments are not necessarily limited to the configuration described above. Further, a part of the configuration of a certain embodiment may be replaced with a configuration of another embodiment, and a configuration of another embodiment may be added to the configuration of a certain embodiment. Further, addition, removal, and replacement of other configurations may be made for one of the configurations of the respective embodiments.

This patent application claims its benefit based on the priority of Japanese Patent Application No. 2015-063639 filed on March 26, 2015, the disclosure of which is incorporated herein by reference.

1‧‧‧Photoresist storage container

2‧‧‧ bag department

2a‧‧‧Receiving Department

3‧‧‧ ring member

3a‧‧‧ openings

4‧‧‧Retaining components

4a‧‧‧ head

4b‧‧‧Clock Department

4c‧‧‧above

4d‧‧‧ side circumference

5‧‧‧ Space Department

8‧‧‧Draining tube

8a‧‧‧Drainage tube hole

9‧‧‧Injection tube

9a‧‧‧Injection tube hole

Claims (10)

A photoresist liquid storage container for storing a photoresist liquid used for photolithography; a flexible bag portion having a storage portion for storing a photoresist liquid; and an injection tube connected to the housing portion for The accommodating portion injects the photoresist liquid; and the discharge tube communicates with the accommodating portion, and discharges the photoresist liquid stored in the accommodating portion out of the photoresist liquid storage container. The photoresist storage container according to claim 1 is a holding member for holding the injection tube and the discharge tube; and the holding member is in a state in which the injection tube and the discharge tube communicate with the receiving portion It is attached to the pocket. A photoresist storage container according to claim 2, wherein the bag portion is provided with an engagement holding portion for engaging with the holding member to mount the holding member to the bag portion. The photoresist storage container according to claim 2, wherein the holding member has a cylindrical shape having an upper surface portion and a side surface portion, and the injection tube is held by the upper surface portion, and the discharge tube is held by the side surface portion. The photoresist storage container according to claim 2, wherein the front end of the injection tube of the housing portion is disposed on the holding member side with respect to the front end of the discharge tube. The photoresist storage container according to any one of claims 1 to 5, wherein the central axis of the injection tube is aligned with a central axis of the discharge tube, and the diameter of the injection tube is larger than the diameter The diameter of the discharge pipe. A photoresist liquid supply device comprising: a photoresist liquid storage container; a flexible bag portion; and a storage portion for storing a photoresist liquid used for lithography; and an injection tube connected to the storage portion; a photoresist is injected into the accommodating portion; and the discharge pipe is connected to the accommodating portion, and the photoresist liquid stored in the accommodating portion is discharged outside the photoresist storage container; and the liquid tank is filled with the tempering temperature The liquid is used to impregnate the photoresist storage container; the temperature adjustment liquid circulation mechanism is configured to circulate the temperature adjustment liquid filled in the liquid tank; the temperature control mechanism controls the temperature of the filled temperature adjustment liquid; The mechanism supplies the photoresist liquid in the photoresist storage container to the photoresist liquid application device. A photoresist liquid coating apparatus comprising: a photoresist liquid storage container; a flexible bag portion; and a storage portion for storing a photoresist liquid used for lithography; and an injection tube connected to the housing portion a photoresist is injected into the accommodating portion; and the discharge pipe is connected to the accommodating portion, and the photoresist liquid stored in the accommodating portion is discharged outside the photoresist storage container; the liquid tank is filled with the liquid Warming liquid to impregnate the photoresist storage container; the temperature adjustment liquid circulation mechanism is to circulate the temperature adjustment liquid filled in the liquid tank; the temperature control mechanism controls the temperature of the filled temperature adjustment liquid; The mechanism supplies the photoresist liquid in the photoresist storage container to the photoresist liquid application device, and drops the nozzle such that the photoresist supplied from the supply mechanism drops down to the surface of the substrate. A photoresist liquid storage device comprising: a photoresist liquid storage container, comprising: a flexible bag portion; and a storage portion for storing a photoresist liquid used for lithography; and an injection tube connected to the storage portion; a photoresist is injected into the accommodating portion; and the discharge pipe is connected to the accommodating portion, and the photoresist liquid stored in the accommodating portion is discharged outside the photoresist storage container; and the liquid tank is filled with the tempering temperature The liquid is immersed in the photoresist storage container; the temperature adjustment liquid circulation mechanism circulates the temperature adjustment liquid filled in the liquid tank; and the temperature control mechanism controls the temperature of the filled temperature adjustment liquid. A method for manufacturing a blank mask, comprising: a process of forming a film for pattern formation on one surface of a substrate; and a process of applying a photoresist solution to the surface of the film by a photoresist coating device and fixing the film; : a step of using a discharge pipe and an injection pipe to generate a circulation by using a discharge pipe and an injection pipe in the photoresist liquid storage container for storing the photoresist; and a step of circulating the temperature adjustment liquid in the bath of the photoresist storage container; The temperature of the temperature regulating liquid in the bath is controlled at a temperature suitable for the temperature of the photoresist coating; and the step of supplying the photoresist suitable for the coating temperature to the photoresist coating device.