KR100680553B1 - Method for peeling positive type resist film, method for manufacturing exposure mask, and resist peeling device - Google Patents

Abstract

 A method of manufacturing a positive film peeling method and a mask for exposure, which can be processed at low cost without requiring special management based on fire methods or various environmental methods, and does not require a large-scale large-scale processing apparatus for a large-sized substrate, and A resist stripping apparatus is disclosed. The positive resist film is peeled off from the substrate by exposing the resist film surface of the substrate having the positive resist film and bringing the exposed resist film into contact with a treatment solution for dissolving the exposed resist. A patterning process is performed by forming a predetermined positive resist pattern on a mask blank on which a thin film made of a transfer mask pattern is formed on a substrate, etching the exposed thin film using the resist pattern as a mask, and performing a patterning process. After exposing the resist pattern by moving the light irradiation means relative to the predetermined direction, the resist pattern is peeled off by being brought into contact with the processing liquid for dissolving the exposed resist. The exposure chamber of a resist stripping apparatus irradiates light to a resist film surface. The processing chamber supplies a processing liquid for dissolving the exposed resist to the resist thin surface of the substrate, and exfoliates and removes the exposed resist. The substrate conveying means conveys the substrate from the exposure chamber to the processing chamber.

Mask, resist

Description

METHOD FOR PEELING POSITIVE TYPE RESIST FILM, METHOD FOR MANUFACTURING EXPOSURE MASK, AND RESIST PEELING DEVICE}

1 is a view showing a manufacturing process of an exposure mask according to an embodiment of the present invention.

2 is a view showing a manufacturing process of a conventional mask for exposure.

3 is a front view of a resist stripping apparatus according to an embodiment of the present invention.

4 is a side cross-sectional view of the loading / unloading seal of the resist stripping apparatus according to the embodiment of the present invention.

5 is a side cross-sectional view of an exposure chamber of a resist stripping apparatus according to an embodiment of the present invention.

6 is a side cross-sectional view of the processing chamber of the resist stripping apparatus according to the embodiment of the present invention.

7 is a schematic diagram of a CPA coater.

* Explanation of symbols for the main parts of the drawings

S11: mask blank preparation process

S12: resist film forming process

S13: exposure process

S14: Developing Process

S15: etching process

S16: exposure process

S17: Treatment Process with Developer

1: resist stripping apparatus

2: loading / unloading seal

3: exposure room

4: treatment room

20: substrate

30: shower nozzle

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of peeling a positive resist film used in a manufacturing process of an image device such as a photo mask, a semiconductor device, or a liquid crystal display device, a method of manufacturing an exposure mask using a positive resist film, and a resist peeling device.

As a conventional technique, the manufacture of a semiconductor device or a display device is performed by the lithographic technique using a photo mask. The photo mask is formed by forming a fine pattern (transfer pattern) made of a thin film of metal or the like on a substrate such as glass, and is subjected to a transfer object (device with a resist film) by an exposure apparatus (pattern transfer apparatus) on which a photo mask is mounted. And pattern transfer of a fine pattern onto a substrate).

The semiconductor device is generally manufactured using a reduced projection exposure apparatus (stepper), in which case the pattern on the photo mask is reduced and projected to a size of, for example, 1/5. On the other hand, in manufacture of display apparatuses, such as a liquid crystal display (LCD), the mask array which is an exposure apparatus using the other system of the same multiple times of exposure is used. The stepper photomask and the mask array photomask are different in size from each other. Stepper photo masks (reticules) are generally square of 5 inches (127 mm x 127 mm) or 6 inches (152.4 mm x 152.4 mm), but in the case of photo masks for mask arrays, Based on the size of the TV display screen, the rectangular one is common, and the size is also larger than that of the reticule (one side 300 mm or more), so it is called a large mask. In addition, the large size mask tends to be larger in size due to the large area of the display screen and the requirement of manufacturing multiple screens once.

By the way, the said photo mask can be obtained by forming a predetermined | prescribed fine pattern in the said thin film using the mask blank which formed the said thin film on the board | substrate used as the original board. A general manufacturing process of the photo mask will be described below with reference to FIG. 2.

First, a mask blank in which a light-shielding thin film made of a material such as a metal or an alloy thereof is formed on a transparent substrate such as quartz glass (S21). Subsequently, a resist film is formed on the entire surface of the mask blank (S22). Typically, a resist film is applied onto the mask blank, followed by heat treatment (pre-baking). As resists, there are two types of negative resists in which the exposed part is cured by a crosslinking reaction and the like and insoluble in the developer, and a positive resist in which the exposed part is made low in molecular weight and dissolved in the developer. Positive type resists are widely used in accordance with the demand for high miniaturization.

Subsequently, a predetermined pattern film surface exposure is performed on the mask blank with the resist film (S23), and a development process is performed using a developer (S24) to form a resist pattern on the mask blank.

Thereafter, the exposed light-shielding thin film is removed by etching using the resist pattern as a mask (S25). Thus, the photomask in which the light shielding thin film was formed on the predetermined pattern on the board | substrate is completed. The remaining resist pattern is peeled off using a dedicated resist stripping solution (S26).

In addition, in addition, in the manufacture of the reflective mask which formed the multilayer reflective film which reflects exposure light on the board | substrate, and the absorber film | membrane on the pattern which absorbs exposure light, or the phase shift mask which formed the phase shift film on the board | substrate, or liquid crystal display device, Although a light shielding part, a gray tone part, and a gray tone mask which formed the light shielding part on the board | substrate used are known, such a photo mask is also manufactured using the same photolithographic process as mentioned above.

In addition, also in the manufacture of a video device such as a semiconductor device or a liquid crystal display device using a photo mask, a photolithographic process is used.

By the way, after finishing the photolithographic process, the resist pattern which became unnecessary is generally stripped off using the above-mentioned dedicated resist stripping solution (sold by the resist manufacturer). Further, Japanese Patent Application Laid-Open No. 2000-147793 discloses the removal of a photoresist film which oxidizes and removes the photoresist film by contacting the ozone gas and the photoresist film removal solution (or the ozone gas-containing photoresist film removal solution) with the photoresist film. A method is disclosed.

However, in the case of the method using the above-mentioned dedicated resist stripping solution, there is no particular problem in resist stripping itself. However, since the components of the resist stripping solution use chemicals that are managed by fire methods or various environmental laws, the management of unused resist stripping solutions Of course, strict management is also required in the waste liquid, and the waste liquid treatment cost increases. In particular, in the case of a large-sized mask, since the board | substrate size is large, the usage-amount of a resist stripping liquid is needed in large quantities, and in recent years, the problem becomes more serious in accordance with the tendency of substrate size enlargement.

In the case of the method of removing the photoresist film disclosed in Japanese Patent Laid-Open No. 2000-147793, for example, pure water, an acidic aqueous solution or an alkaline aqueous solution may be used as the photoresist film removing solution. Although no special management is required, and it is improved also in terms of the environment, an ozone gas supply pipe or a treatment tank for recovering and treating the ozone gas and / or photoresist film removal solution is provided. Since an expensive dedicated photoresist film removal device made of a sealed container for preventing gas, vapor, and the like generated in the form from being discharged as it is, is required, it becomes a factor to increase the cost.

As a method of solving the above-described problems, for example, Japanese Patent Laid-Open No. Hei 6-164101 discloses a method of exposing a resist pattern remaining by irradiating ultraviolet rays and peeling the resist pattern by developing. In order to completely remove resist residues, a method is disclosed in which ultraviolet rays are irradiated with an ultraviolet irradiation lamp while rotating a substrate, and the reflected light is irradiated onto the entire surface of the resist film by a reflector provided on the inner wall of the exposure chamber.

However, the method described in Japanese Patent Laid-Open No. 6-164101 requires a device having a rotating mechanism, for example, when processing a large substrate such as a liquid crystal panel or a large mask used in the manufacture thereof, a large-scale large processing apparatus. There is a problem that is required.

Accordingly, an object of the present invention is to solve the problems in the prior art, and does not require special management based on fire methods or various environmental laws, and can be processed at low cost, and also requires a large-scale large-scale processing apparatus for a large substrate. The present invention provides a method of peeling a positive film which is not used, a method of manufacturing a mask for exposure, and a resist peeling device.

In order to achieve the said objective, this invention has the following structures.

In the configuration 1, after exposing the resist film surface by relatively moving the resist film surface and the light irradiation means of the substrate having the positive resist film in a predetermined direction, the exposed resist film is brought into contact with the processing liquid for dissolving the exposed resist. It is a peeling method of a positive resist film characterized by peeling and removing the said positive resist film from a board | substrate.

In the configuration 2, the substrate having the positive resist film is formed on a thin film formed on the substrate by forming a predetermined pattern by performing a patterning process including an exposure process and a developing process of a positive resist film, and then the remaining positive resist remains. It is a board | substrate which has a film | membrane, It is the peeling method of the positive resist film of the structure 1 characterized by the above-mentioned.

Configuration 3 is a peeling method of the positive resist film of Configuration 2, wherein the developer used in the development step is used as the treatment solution.

In the configuration 4, a patterning process is performed by forming a predetermined positive resist pattern on a mask blank on which a thin film made of a transfer mask pattern is formed on a substrate, and etching the exposed thin film using the resist pattern as a mask. A method of manufacturing an exposure mask, comprising: exposing the resist pattern by moving the resist pattern remaining after the patterning step and the light irradiation means relatively in a predetermined direction, and then contacting the resist with a processing liquid for dissolving the exposed resist. It is a manufacturing method of the mask for exposure characterized by peeling and removing a pattern.

In the configuration 5, using the developing solution used when forming a predetermined resist pattern on the mask blank as the processing liquid, and contacting the developing solution using the developing means when forming a predetermined resist pattern on the mask blank. It is a manufacturing method of the mask for exposure of the structure 4 characterized by the above-mentioned.

Configuration 6 is a resist stripping apparatus for exfoliating and removing the positive resist film from the substrate by exposing the resist thin surface of the substrate having the positive resist film and then contacting the exposed resist film with a processing liquid that dissolves the exposed resist, An exposure chamber including holding means for holding the substrate and light irradiation means provided opposite the resist thin surface of the substrate; A processing chamber having holding means for holding the substrate and processing liquid supplying means for supplying a processing liquid for dissolving the exposed resist on the resist thin surface of the substrate, the processing chamber for peeling and removing the exposed resist; And a substrate conveying means for conveying the substrate from the exposure chamber to the processing chamber.

In the configuration 7, the holding means for holding the substrate in the exposure chamber and the processing chamber is inclined and held so that the resist thin surface of the substrate is inclined upwardly.

According to the structure 1, the positive type resist film peeling method of this invention exposes the resist film surface of the board | substrate which has a positive resist film, and then contacts the exposed resist film with the process liquid which melt | dissolves an exposed resist, and the said positive resist film | membrane is removed from the said board | substrate. The type resist film is peeled off.

When the positive resist is exposed to light, the main chain of the polymer is cut by the irradiation energy to reduce the molecular weight, thereby making it soluble in a predetermined treatment liquid. Therefore, according to the method of the configuration 1, the positive resist film can be peeled off and removed from the substrate by a step of exposing the resist film and then contacting the resist film with a predetermined treatment liquid. Becomes possible. In addition, since the treatment liquid for dissolving the exposed resist does not require special management based on a fire method or various environmental methods, it is possible to reduce costs due to waste liquid treatment and the like. Moreover, according to the configuration 1, the resist film surface is exposed by relatively moving the resist film surface and the light irradiation means in a predetermined direction, so that the entire surface of the resist can be irradiated onto the large substrate without using a rotating mechanism.

For example, as in the configuration 2, the thin film formed on the substrate is subjected to a patterning process including an exposure process and a development process of the positive resist film to form a predetermined pattern, and then the remaining positive resist film is formed using the method of the composition 1 Can be peeled off. The positive resist film in this case is a resist film on a pattern formed on a thin film on a substrate. The exposed thin film is removed by etching using the resist pattern as a mask, and a predetermined pattern is formed on the thin film on the substrate. In this manner, after the predetermined pattern is formed on the thin film on the substrate, the remaining resist pattern becomes unnecessary and needs to be removed. Therefore, only the resist pattern can be peeled off from the substrate by exposing the remaining resist pattern by the method of Configuration 1 and then bringing the resist pattern into contact with a predetermined processing liquid.

In addition, according to the configuration 3, the remaining positive resist film can be peeled off by using the developing solution used in the developing step as the processing liquid.

Therefore, according to the method of the structure 3, the peeling method of the remaining resist pattern from the board | substrate can respond to the developing process at the time of forming a predetermined | prescribed resist pattern on the thin film on a board | substrate. In addition, since the developer of the positive resist generally used does not need special management based on the fire method or various environmental methods, it is possible to reduce the cost due to waste liquid treatment or the like. In addition, since the developer of a positive resist is used when peeling and removing a resist pattern, there is no possibility of changing the thin film on a board | substrate.

In addition, according to the configuration 4, a patterning process is performed by forming a predetermined positive resist pattern on a mask blank on which a thin film made of a transfer mask pattern is formed on a substrate, and etching the exposed thin film using the resist pattern as a mask. As a method of manufacturing an exposure mask which performs the step, after exposing the resist pattern remaining after the patterning step, the resist pattern can be peeled off by being brought into contact with a processing liquid for dissolving the exposed resist. That is, the resist pattern can be processed at low cost by using the step of exposing and then the step of contacting with the processing liquid. Further, according to the configuration 4, the resist film surface is exposed by moving the resist film surface and the light irradiation means relatively in a predetermined direction, so that the entire surface of the resist can be irradiated to the entire surface of the resist even without using a rotating mechanism. have.

In addition, according to the configuration 5, as the processing liquid, the developer used when forming a predetermined resist pattern on the mask blank is used, and the developing means when forming a predetermined resist pattern on the mask blank is used. By contacting with a developing solution, resist peeling can be handled by a developing apparatus. In addition, since the developer of the positive resist generally used does not require special management based on the fire method or various environmental methods, it is possible to reduce the cost due to waste liquid treatment or the like. In addition, since the developer of the positive resist is used when the resist pattern is peeled off, there is no fear of altering the transfer mask pattern formed on the substrate.

Moreover, according to the resist stripping apparatus of the structure 6, a positive resist film can be peeled off and removed from a board | substrate by performing a process of a resist film by the exposure chamber which irradiates a resist film with a light, and the process chamber which supplies a predetermined process liquid to a resist film. The process can be used at low cost. Furthermore, by using the substrate conveying means, light irradiation to the resist film and processing with the processing liquid can be continuously performed.

In addition, according to the configuration 7, the holding means for holding the substrate in the exposure chamber and the processing chamber is kept inclined so that the resist film surface of the substrate faces the inclined direction, so that the space of the resist film surface of the substrate is directly above (horizontal). Since it can abbreviate | omit, it is especially suitable for the process of a large substrate.

Hereinafter, embodiments of the present invention will be described in detail.

Examples of the present invention include the following examples.

[First Embodiment]

A first embodiment of the present invention is a method of peeling a positive resist which exfoliates and removes the positive resist film from the substrate by exposing the resist film surface of the substrate having the positive resist film and then contacting the exposed resist film with a developer. In the first embodiment, a developing solution used for developing a positive film is used as the treating solution for dissolving the exposed resist film.

In the first embodiment, as the positive resist film formed on the substrate, for example, a pattern including a step of forming a predetermined resist pattern on a thin film formed on the substrate by an exposure process and a developing process of the positive resist film. By carrying out the formation process, a positive resist film remaining after forming a predetermined transfer mask pattern or a positive resist film which fails to apply resist can be mentioned. As a form of forming a thin film of a single layer or a plurality of layers on a substrate and forming a predetermined transfer mask pattern on the thin film, an exposure mask or a semiconductor device used for manufacturing a semiconductor device or a liquid crystal display device, or a liquid crystal display device ( Liquid crystal display panels); According to the first embodiment, in the manufacturing process of the above-mentioned exposure mask or various apparatuses, when resist coating fails and the resist coating needs to be applied again, the poor positive resist film can be peeled off and removed. After the photo process is finished, the remaining unnecessary positive resist film can be peeled off.

For example, the resist film contacts a coating liquid raised from a nozzle using a capillary phenomenon with respect to a spin coater, a slit coater, or a downwardly applied coating surface, and moves the substrate and the nozzle relative to each other, thereby applying a predetermined amount of resist to be applied. It is possible to apply using a CAP coater or the like.

Examples of the positive membrane include a dissolution inhibiting type consisting of a main chain cleavage resist made of a relatively high viscosity polymer resin of polybutene-1-sulfone or polyglycidyl methacrylate, or a novolak resin and a dissolution inhibitor. Resists and the like are known.

The exposure process is performed on the positive resist film remaining on the substrate by performing a poor positive resist film or a patterning process that fails to apply resist, so as to obtain solubility in a developer, and then supplying a developer is unnecessary. The resist film is peeled off.

In this case, the exposure wavelength is preferably a wavelength belonging to the photosensitive wavelength region of the positive resist. In particular, exposure light in a wavelength range having high sensitivity to the positive resist may be irradiated. In addition, since the exposure amount is for the purpose of resist stripping removal, it is preferable to give more exposure amount than the exposure amount normally required for forming a resist pattern, for example. In particular, the resist pattern used in the etching mask may have a surface modified layer formed on the resist pattern by etching, and therefore, in order to remove the surface modified layer, it is preferable to give an exposure amount higher than the exposure amount normally required to form the resist pattern. Do.

The exposure method uses a method of exposing the resist film surface by moving the resist film surface and the light irradiation means of the substrate having the positive resist film relative to the predetermined direction. Specifically, by moving the substrate or the light irradiation means by using the light irradiation means extending in one direction of the substrate, the light irradiation means is scanned on the substrate to expose the entire surface of the resist film on the substrate. By using the above method, light irradiation can be easily performed on a large substrate, and light irradiation can be performed continuously on a plurality of substrates.

According to the first embodiment, in the peeling of the resist using the method of irradiating light to the resist film from above the substrate, for example, on the side or the rear surface of the substrate as in the resist film coated using the CAP coater It is especially suitable for peeling of the resist film apply | coated by the application | coating method which a resist does not enter.

It is preferable that the developing solution used after an exposure process is a developing solution corresponding to a positive resist material. In addition to the developer exclusively used for the positive resist material to be used, the resist is stripped and removed. The developer may not necessarily be a developer, and most importantly, a treatment liquid capable of dissolving the exposed positive resist material. For example, a developer mainly containing an alkali substance such as sodium hydroxide (NaOH) and potassium hydroxide (KOH) is preferably used. Since none of these developing solutions uses chemicals that are subject to management in fire fighting methods or various environmental laws, no special management is necessary and the handling is easy.

In addition, there is no restriction | limiting in particular in the method of making it contact with a developing solution in this case, For example, the method of submerging a board | substrate with a resist film in a developing solution, or the method of supplying a developing solution to a shower image from the board | substrate with a resist film, or a developing solution Suction and pull into the nebulizer may be optionally applied.

Second Embodiment

According to a second embodiment of the present invention, a predetermined positive resist pattern is formed on a mask blank on which a thin film of a transfer mask pattern is formed on a substrate, and the exposed thin film is etched using the resist pattern as a mask, thereby forming a pattern. It is a manufacturing method of the exposure mask which peels and removes a resist pattern by performing a chemical conversion process, exposing the remaining resist pattern, and making it contact with a developing solution.

The second embodiment is an embodiment of a method of peeling and removing a resist pattern that is no longer necessary in the manufacturing process of the exposure mask.

 1 is a view showing a manufacturing process of an exposure mask according to an embodiment of the present invention.

First, a mask blank in which a thin film (for example, a light shielding film) formed of a transfer pattern for transferring to a transfer object (for example, a semiconductor substrate) is formed on a substrate is prepared (S11).

Examples of the mask blank mentioned in the present invention may be a transmissive mask blank or a reflective mask blank, the structure of which is a thin film made of a transfer pattern to be transferred to the transfer target by causing optical changes to exposure light on the substrate. Have

The transmissive mask blank uses a light transmissive substrate such as an organic substrate as the substrate. An optical change with respect to the exposure light refers to a light shielding film that blocks the exposure light, or a phase shift film that changes the phase of the exposure light (the phase shift film includes a halftone film having a light shielding function and a phase shift function). Accordingly, the transmissive mask blank includes a photo mask blank on which a light shielding film is formed, a phase shift mask blank on which a phase shift film (including a half tone film) is formed, and the like.

In addition, in addition to that, a creton mask having a light shielding portion, a semi-transmissive portion, and a light transmitting portion formed on a substrate, which is used in the manufacture of a liquid crystal display device, is known. It also includes a mask blank on which a film and a light shielding film are formed.

In addition, the reflective mask blank is a mask blank which uses a thing with a small coefficient of thermal expansion as a board | substrate, and has a light absorber film | membrane which consists of a light reflection multilayer film and a transfer pattern on the said board | substrate. In this case, what causes an optical change with respect to exposure light refers to the light reflection multilayer film which reflects exposure light, the light absorber film which interrupts exposure light, etc.

Such a mask blank (substrate with a thin film) is produced by forming a thin film made of a transfer pattern on the substrate by a sputtering method, a vapor deposition method, a CVD method, or the like.

Subsequently, a positive resist film is formed on the entire surface of the mask blank (S12). Formation of the said positive resist film is performed by apply | coating the resist coating liquid prepared by melt | dissolving a positive resist material in a solvent and preparing it with the moderate viscosity on a mask blank. Usually, a resist film is apply | coated on a mask blank, and heat processing (preliminary baking) is performed.

Subsequently, a predetermined pattern drawing (exposure) is performed on the mask blank with the positive resist film (S13), and a developing process is performed using a developing solution (S14) to form a resist pattern on the mask blank. The exposure at the time of forming a resist pattern is a scanning exposure by the laser drawing apparatus which has a short wavelength laser light source normally.

Thereafter, the exposed thin film is removed by etching using the resist pattern as a mask (S15). In the case of the reflective mask, the light absorber film of the uppermost layer is formed on the pattern.

In this way, the exposure mask in which the thin film was formed on the board | substrate on the predetermined pattern is completed. The resist pattern which became unnecessary is peeled off by performing exposure process S16 and the processing process S17 by the developing solution in the same method as the above-mentioned embodiment. At this time, it is preferable to perform the development process at the time of forming a predetermined | prescribed resist pattern on the said mask blank again, and to make the resist pattern remaining after exposure contact with a developing solution. Thereby, resist peeling can be handled during the patterning photo process, and process simplicity can be aimed at. In addition, there is no need to provide a line for a resist peeling step in particular, and the facility surface can be simplified. Moreover, it is also preferable to contact the developing solution with the resist pattern remaining after exposure using the developing means at the time of forming a resist pattern.

However, exposure conditions (exposure wavelength, exposure amount, exposure method, etc.) and development conditions (type of developer, development time, development method, etc.) performed to peel off a resist pattern are exposure at the time of forming a resist pattern. The conditions and development conditions may be the same, but may be different. The exposure conditions and development conditions to be carried out to remove the resist pattern are not necessarily set as strictly as the exposure conditions and development conditions at the time of forming the resist pattern.

In addition, since an exposure amount aims at peeling a resist, it is preferable to provide more than normally the exposure amount required for resist pattern formation (for example, 2 times or more). In the manufacture of a photomask having a chromium (Cr) light shielding film on a substrate, the resist pattern surface is modified by etching liquid (generally dicerium ammonium acetate and perchloric acid) used for wet etching of chromium, and then exposed by exposure. Since it may be difficult to do so, by increasing the exposure dose and applying strong energy, the removal of the resist pattern can be facilitated.

Moreover, since the image development method in the case of peeling and removing a resist pattern aims at peeling a resist from a board | substrate, many may be processed at once and may be processed continuously in an in-line system.

Moreover, in the Example of this invention, by providing an exposure means to the developing apparatus used for peeling removal of a resist pattern, the peeling removal process of the resist pattern including exposure and the process by a developing solution can be performed continuously in the same apparatus. Moreover, by providing a developing apparatus and an exposure apparatus in parallel, it can carry out continuously by the conveyance between apparatuses in which the peeling removal process of the resist pattern including the process of exposure and a developing solution is provided in parallel.

Third Embodiment

The third embodiment of the present invention is a resist for exfoliating and removing a positive resist film from the substrate by exposing the resist film surface of the substrate having the positive resist film and then contacting the exposed resist film with a treatment solution for dissolving the exposed resist. A peeling apparatus, comprising: an exposure chamber having holding means for holding the substrate and light irradiation means provided opposite to a resist film surface of the substrate; A processing chamber including holding means for holding the substrate and processing liquid supply means for supplying a processing liquid for dissolving the exposed resist on the resist film surface of the substrate, the processing chamber for exfoliating and removing the exposed resist; And a substrate conveying means for conveying the substrate from the exposure chamber to the processing chamber.

3 is a front view of the resist stripping apparatus according to the third embodiment, FIG. 4 is a side cross-sectional view of the loading / unloading seal of the resist stripping apparatus according to the third embodiment, and FIG. 5 is a resist stripping according to the third embodiment. 6 is a side cross-sectional view of the exposure chamber of the apparatus, and FIG. 6 is a side cross-sectional view of the processing chamber of the resist stripping apparatus according to the third embodiment.

4 to 6, the resist stripping apparatus 1 of the third embodiment is inclined at a predetermined angle α so that the upper surface of the substrate 20 can be inclined to be inclined upward. .

3, in the resist peeling apparatus 1, the loading / unloading chamber 2, the exposure chamber 3, and the processing chamber 4 are provided in order from the right side in the figure. In addition, a plurality of support coaters 12 are provided at substantially constant intervals in the vertical direction along the back surface of each thread. Each support coater 12 is rotatably supported by a holding shaft 13 arranged in the vertical direction. Moreover, the many support coater 12 which has the same structure also in the left-right direction is arrange | positioned along the back surface. Thereby, each support coater 12 is made to be rotatable about the holding shaft 13 parallel to the said back surface 1B. Thus, when the board | substrate 20 is mounted on the several support coaters 12 arrange | positioned along the back surface 1B inside each chamber, the back surface of the board | substrate 20 (the surface on the opposite side to the main surface, ie, the resist film surface and Since the opposite side) contacts the circumferential surface of each support coater 12, the substrate 20 can move (slid) in the loading / unloading chamber 2 in the up-and-down direction. Moreover, the conveyance coater 14 rotatable about the axis | shaft perpendicular to the said back surface 1B is arrange | positioned at the lower end of the board | substrate 20, and the lower end of the board | substrate 20 is the circumference | surroundings of the said transfer coater 14 By holding in contact with the holding tank 14A provided on the surface, the substrate 20 can be moved in the horizontal direction by rotating the transfer coater 14. Thus, since it is a structure which hold | maintains the lower end of the board | substrate 20, it can use also about the board | substrate with which size differs.

Next, each thread is demonstrated in detail.

As shown in FIG. 4, the loading / unloading seal 2 has a box shape in which the front side 1A side is opened to allow entry and exit of the substrate 20 mounted on the transport coater 14.

Subsequently, as shown in FIG. 5, the exposure chamber 3 adjacent to the loading / unloading chamber 2 has light irradiation means such as an ultraviolet lamp on the inner wall surface facing the surface of the substrate 20 on the front side 1A side. 15)

Next, as shown in FIG. 6, in the processing chamber 4 adjacent to the exposure chamber 3, as the processing supply means, one side direction of the substrate 20 (in the third embodiment, the inclined direction of the substrate 20). The shower nozzle 30 (refer FIG. 3) which can supply a process liquid almost evenly with respect to phosphorus up-down (vertical) direction is arrange | positioned. In addition, the shower nozzle 30 is arranged parallel to the main surface of the substrate 20 at a predetermined interval, and on the main surface of the substrate orthogonal to the one side direction, that is, in the third embodiment, The scanning operation is performed on the main surface in the left and right directions (solid line direction described in FIG. 3). The shower nozzle 30 is formed in a tubular shape in its entirety, and a plurality of nozzle balls 31 (see FIG. 6, moreover, in FIG. 6) are shown on the surface of the nozzle nozzles 31 at substantially equal intervals along the long direction. Is omitted), and after the shower nozzle 30 is treated with a predetermined hydraulic pressure, for example, when a developer is supplied, the developer is ejected onto the shower in each nozzle hole 31 of the shower nozzle 30. . In the third embodiment, since the shower nozzle 30 is arranged in the longitudinal direction over the vertical direction of the substrate 20, the processing liquid can be supplied almost evenly with respect to the vertical direction of the substrate 20. Then, by scanning the shower nozzle 30 on the main surface in the vertical direction, the processing liquid can be almost evenly filled in the entire area of the main surface of the substrate 20.

Next, the procedure of peeling a resist using the resist peeling apparatus 1 of 3rd Example is demonstrated. First, the board | substrate 20 which has a resist film which peels on the conveyance coater 14 of the loading / unloading chamber 2 is mounted. Thereafter, the transfer coater 14 is rotated at a constant speed, and the substrate 20 is sent to the exposure chamber 3 at a constant speed and passed through. At this time, the light irradiation means 15 of the exposure chamber 3 is in a state where the power supply is turned on. The board | substrate 20 which passed the exposure chamber 3 is conveyed to the process chamber 2, and stops. Next, the resist is peeled off by supplying the treatment liquid to the entire surface of the substrate 20 using the shower nozzle 30. Furthermore, rinsing is performed by supplying pure water to the entire surface of the substrate 20 using the shower nozzle 30. Thereafter, the transfer coater 14 is rotated in reverse to move the substrate 20 in the direction of the loading / unloading chamber 2, and the exposure chamber 3 in which the power supply of the light irradiation means 15 is turned off. After passing through, the substrate 20 is taken out after the loading / unloading chamber 2 is stopped. By such a procedure, the light irradiation to the resist film and the treatment with the treatment liquid can be continuously performed.

According to the resist stripping apparatus 1 of the third embodiment, the inclination angle can be increased also for the large substrate, so that the space can be formed. As can be seen with reference to Figs. 4 to 6, in the case of the resist stripping apparatus 1 of the third embodiment, the depth D of the apparatus is completed smaller than the substrate size. From this point of view, the inclination angle of the substrate as described above is more than 25 degrees, preferably more than 45 degrees, more suitable for large substrates. In addition, even if the inclination angle of the substrate is increased, the treatment liquid can be supplied to the entire region of the main surface of the substrate even if the flow rate of the treatment liquid flows down, so that the treatment with high processing ability and high uniformity can be performed. Therefore, the resist peeling apparatus of this invention is especially suitable when the resist peeling of a large board | substrate with a length of at least 1 side is 300 mm or more. In other words, even a large-sized substrate, processing capability is high by eliminating space, and uniformity is possible in the resist stripping process.

In addition, in the third embodiment, the loading / unloading chamber 2 and the exposure chamber 3, the exposure chamber 3 and the processing chamber 4 are arranged adjacent to each other, but each having a separate function is disposed between them. It may be arranged. For example, you may provide the drying chamber which supplies air between the exposure chamber 3 and the process chamber 4, and may dry the board | substrate after image development rinse. In addition, you may have other functions in each room.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described more concretely by embodiment.

(1st embodiment)

A chromium film and a chromium oxide film are sequentially laminated on a synthetic quartz glass substrate having a substrate size of 330 mm x 450 mm by sputtering to obtain a large mask blank for manufacturing a liquid crystal display device in which a light shielding film and an antireflection film are formed on the substrate.

On the obtained mask blank, a positive resist liquid is rotationally apply | coated using a spinner (rotary coating apparatus), and a positive resist film is formed. As a positive resist, a high molecular weight resist PBS (polybutene-1-sulfone) is used, and this dissolved in methylcellosorbate is used as a resist liquid. Moreover, after apply | coating the said resist liquid, predetermined heat-drying process is performed using a heat-drying apparatus.

Subsequently, the mask blank with a positive resist film is exposed by exposure apparatus (laser drawing apparatus), and then developed by a developing solution containing potassium hydroxide (KOH) as a main component, and a predetermined resist on the mask blank. Form a pattern. In addition, the said developing process is performed at 23 degreeC for 60 second.

Thereafter, the exposed chromium oxide film and the chromium film are removed by a wet etching process as a mask, and a chromium light shielding film and an antireflection film are formed on a predetermined pattern on the substrate. The etching solution uses an aqueous solution of dicerium ammonium diacetate and perchloric acid.

Subsequently, in order to peel off and remove the remaining resist pattern, the process with an exposure process and a developing solution is performed. In this case, the exposure treatment is performed by exposing the entire surface using an exposure apparatus using a mercury lamp as a light source. In order to consider that the resist pattern surface is modified by the etching solution, the exposure time is set to be longer than the exposure amount necessary for forming the resist pattern. In addition, the process by a developing solution is performed on the conditions similar to the image development at the said resist pattern formation. In this way, the remaining resist pattern can be peeled off by performing an exposure process and a process using a developer.

By performing it as mentioned above, the transmissive type mask (large mask for liquid crystal display device manufacture) which has the chromium light shielding film and the anti-reflective film formed on the predetermined pattern on the glass substrate is obtained.

(2nd embodiment)

On the large-sized mask blank for liquid crystal display device manufacturing manufactured similarly to 1st Embodiment, application | coating of a resist is performed using a CAP coater, and the CAP coater used by 2nd Embodiment is specifically, an apparatus as shown in FIG. And the nozzle 43 having a capillary gap W in the liquid tank 42 filled with the resist liquid 41 is locked, and the nozzle 43 is raised to raise the main surface downward. The substrate 40 is shown while contacting the main surface of the substrate 40 with the resist liquid 41 positioned near the main surface of the substrate and raised to the tip of the nozzle 43 using the capillary phenomenon in the gap W on the capillary tube. The resist film is applied to the surface of the substrate 40 by moving in the seal direction. When such a coating method is used, the resist is not applied to the side or rear surface of the substrate so that the resist sheet peeling method of the present invention can be suitably used.

Subsequently, with respect to the mask blank with the positive resist film, a predetermined resist pattern is formed in the same manner as in the first embodiment, and the chromium oxide film and the chromium film are etched using the resist pattern as a mask, and on the substrate. The chromium film and the antireflection film are formed on a predetermined pattern.

Thereafter, in order to peel off and remove the remaining resist pattern, the resist stripping apparatus described in the third embodiment is used. In addition, exposure conditions are appropriately set in an exposure chamber, and the process liquid supplied from a process chamber uses the developing solution at the time of resist pattern formation. In this manner, the resist pattern remaining can be peeled off by continuously performing light irradiation to the resist pann and processing using a developer using a resist stripping apparatus.

As described above, a transmissive mask (large mask for liquid crystal display device manufacture) having a chromium light shielding film and an antireflection film formed on a glass substrate in a predetermined pattern can be obtained.

In addition, in the above embodiment, in the manufacturing process of one example of the transmissive exposure mask, the case where the positive removal of the positive resist film according to the present invention is described is described, but the present invention is not limited to the related examples. For example, also in the manufacturing process of the said phase shift mask, a gray tone mask, or a reflective type exposure mask, peeling removal of the positive resist film which concerns on this invention can be carried out. In addition, although not shown in the Example, also in the manufacturing process of a semiconductor device or a liquid crystal display device, the positive resist film which remains according to a photolithographic process can be peeled off by this invention.

 According to the present invention, a step of exposing a resist film and then contacting the exposed resist film with a processing liquid for dissolving the exposed resist is carried out in order to exfoliate and remove unnecessary positive resist film remaining on the substrate from the substrate. . As a result, the positive resist film can be peeled off from the substrate and can be processed at low cost using a simple process. In addition, in the present invention, since the developer used in the developing step can be used as a treatment liquid for carrying out the positive resist film stripping method, it can be performed without using a special chemical for peeling the resist film. Moreover, since the developer of the positive resist generally used does not require special management based on the fire method or various environmental methods, the waste liquid treatment and the like can be performed at a normal level, thereby reducing the cost due to the waste liquid treatment and the like. Further, according to the present invention, since the resist film surface is exposed by moving the resist film surface and the light irradiation means relatively in a predetermined direction, light can be irradiated to the entire surface of the resist on the large substrate without using a rotating mechanism. .

In addition, by applying the positive resist film peeling method according to the present invention, it is possible to reduce the manufacturing cost of the exposure mask.

Claims (7)

After exposing the resist film surface by moving the resist film surface of the substrate having the positive resist film and the light irradiation means relative to each other, the exposed resist film is brought into contact with the processing liquid for dissolving the exposed resist. A peeling method of a positive resist film, characterized in that the positive resist film is peeled off. The remaining positive type of claim 1, wherein the substrate having the positive resist film is formed by performing a patterning process including a process of exposing and developing a positive resist film to a thin film formed on the substrate. It is a board | substrate which has a resist film, The peeling method of the positive type resist film characterized by the above-mentioned. 3. The method of peeling a positive resist film according to claim 2, wherein a developing solution used in the developing step is used as the treating solution. A method of manufacturing an exposure mask which performs a patterning process by forming a positive resist pattern on a mask blank on which a thin film made of a transfer mask pattern is formed on a substrate, and etching the exposed thin film using the resist pattern as a mask. As After exposing the resist pattern by moving the resist pattern remaining after the patterning process and the light irradiation means relative to each other, the resist pattern is peeled off by contacting with the processing liquid for dissolving the exposed resist. The manufacturing method of the mask for exposure made into. 5. The developer according to claim 4, wherein a developing solution used for forming a resist pattern on the mask blank is used as the processing solution, and contacting with the developing solution is carried out by using a developing means for forming the resist pattern on the mask blank. The manufacturing method of the mask for exposure characterized by the above-mentioned. A resist stripping apparatus for exfoliating and removing a positive resist film from a substrate by exposing a resist thin surface of a substrate having a positive resist film and then contacting the exposed resist film with a processing liquid that dissolves the exposed resist. An exposure chamber including holding means for holding the substrate and light irradiation means provided opposite the resist thin surface of the substrate; A processing chamber having holding means for holding the substrate and processing liquid supplying means for supplying a processing liquid for dissolving the exposed resist on the resist thin surface of the substrate, the processing chamber for peeling and removing the exposed resist; And And a substrate conveying means for conveying the substrate from the exposure chamber to the processing chamber. 7. The resist stripping apparatus according to claim 6, wherein the holding means for holding the substrate in the exposure chamber and the processing chamber is inclined so that the resist thin surface of the substrate is inclined upwardly.

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