WO2010116647A1

WO2010116647A1 - Method for forming resist pattern, and device

Info

Publication number: WO2010116647A1
Application number: PCT/JP2010/002139
Authority: WO
Inventors: 上原剛; 青山哲平
Original assignee: 積水化学工業株式会社
Priority date: 2009-04-08
Filing date: 2010-03-25
Publication date: 2010-10-14
Also published as: JP2010243918A; CN102362224A; JP4681662B2

Abstract

Disclosed is a method for forming a resist pattern, wherein the uniformity of development is improved by increasing the wettability of the surface of a resist layer when the resist pattern is formed on a device such as a photoresist. Specifically, a resist layer (93) is formed by applying a photosensitive resist over a substrate (91) (resist application step). Then, the resist layer (93) is partially irradiated with light (light exposure step). After that, a process gas for lyophilization is brought into contact with the resist layer (93) by being expelled through a discharge space (23) at near atmospheric pressure (atmospheric-pressure remote plasma lyophilization step). Then, a developer liquid (5) is brought into contact with the resist layer (93) (development step).

Description

Method and device for forming resist pattern

The present invention relates to a method of forming a resist pattern and a device manufactured by the method, and more particularly to a method of forming a resist pattern suitable for manufacturing a photomask or a color filter as the device.

A photomask is a device used to manufacture electronic elements such as integrated circuits. Since the pattern of the photomask is transferred to the electronic element, the quality of the pattern greatly affects the quality of the electronic element.

An example of a photomask manufacturing process will be described.
A light-shielding film made of chromium or the like is coated on the entire surface of the sufficiently cleaned glass substrate (light-shielding film forming step). A photosensitive resist is applied on the light-shielding film by spin coating or slit coating (resist coating process). The resist can be classified into a positive type and a negative type. The applied resist is pre-baked (initial baking) and then exposed along a desired pattern (exposure process). In a positive type resist, the exposed portion is decomposed and becomes soluble. In a negative resist, the exposed portion is polymerized and becomes insoluble. After exposure, it may be baked again if necessary. Then, a developing solution is made to contact a resist and a pattern is developed (development process). In the case of a positive resist, a developer that dissolves the exposed portion is used. In the case of a negative resist, a developer that dissolves the resist other than the exposed portion is used. As a result, the exposed portion of the positive resist is removed, and the exposed portion of the negative resist remains. After development, the substrate is washed with a rinsing solution to sufficiently remove moisture, and then post-baking (final baking) is performed. The process so far is called a photolithography method. Thereafter, the light shielding film in the portion not covered with the resist is etched (etching step). Then, the resist covering the remaining light shielding film is removed by dissolving it in an organic solvent (resist removing step).
The photolithography method described above is also applied to the production of color filters for liquid crystal displays.

In order to manufacture devices such as photomasks and color filters with excellent quality, it is necessary to clarify the exposed and unexposed portions of the resist and form a resist pattern as designed. Therefore, the exposure process and the development process are particularly emphasized.

The exposure process employs a method in which a resist is directly drawn by irradiating an electron beam on the resist, or a method in which a pattern mask is arranged on the upper side of the resist and ultraviolet rays are irradiated from above the pattern mask. Yes.

The development process is generally performed by any one of the three development methods of dip, shower, and paddle.
Dip development is a development method in which a substrate to be developed is immersed in a developer and rocked. It is often applied to manual development work in the early stage of mass production. In general, a large number of substrates to be developed are collectively attached to a dedicated suspension device.

Shower development is a developing method in which a developing substrate is placed on a roller conveyor and moved across the shower of the developing solution while the developing solution is constantly blown out from a jet nozzle. It is the most common method in devices that perform automated flow operations. One after another, new developer is accelerated and comes into contact with the resist on the surface of the substrate to be developed. For this reason, the developing speed is the fastest among the three developing methods. Further, the amount of developer used per substrate to be developed can be reduced by collecting the developer after spraying and recycling it through a filtration device.

Paddle development is a method in which a developer film is formed on the surface of a substrate to be developed and developed. The film of the developer is formed by dropping the developer on the surface of the substrate to be developed from a slit-shaped opening or spraying it in a mist with a sprayer. Paddle development is the best among the three development methods in terms of development uniformity, and is effective in dealing with development unevenness in shower development.

Patent Document 1 describes that a gas containing oxygen is turned into plasma under the vicinity of atmospheric pressure to ash the photoresist.
Patent Document 2 describes that a gas containing fluoride is discharged at atmospheric pressure to ash the resist.

JP 2003-163207 A Japanese Patent No. 2768760

The above three development methods in the development process have the following problems.
In the dip development, the substrate to be developed is swung in the developer in order to promote the progress of the development, but the flow of the phenomenon liquid on the surface of the substrate to be developed is worse than that in the shower development.

In shower development, the developer shower tends to be non-uniform and uneven development tends to occur. Although there has been devised to prevent the developer from hitting the surface of the substrate to be developed by the arrangement and movement of the shower spout (swinging type, etc.), development unevenness has not been easily solved.

In paddle development, the developer stays at the same position on the surface of the substrate to be developed during the development period. Therefore, the contact between the resist and the developer is static, and the development is performed with almost only chemical reaction force. For this reason, the developing speed is slower than other developing methods. Further, since the developer is stationary on the substrate to be developed, the used developer is deteriorated and the developing power is reduced. There is also a large amount of impurities. Accordingly, it is difficult to circulate and reuse the developer, and it is always necessary to use a new developer. For this reason, the consumption amount of the developer per one substrate to be developed is larger than in other development methods. In particular, when the surface of the resist is uneven, it is necessary to increase the film thickness of the developer, and the consumption of the developer increases more and more.

In order to solve the above-mentioned problems, a resist pattern forming method according to the present invention includes a resist coating process in which a photosensitive resist is applied to a substrate of a device to form a resist layer, and light is partially applied to the resist layer. An exposure process to irradiate;
An atmospheric pressure remote plasma lyophilic process in which a processing gas for lyophilicity is blown through a discharge space near atmospheric pressure and is brought into contact with the resist layer;
A development step of bringing a developer into contact with the resist layer;
Are sequentially executed.
By the atmospheric pressure remote plasma lyophilic step, the surface of the resist layer can be made lyophilic and wettability can be improved. Therefore, in the subsequent development process, the developer can be uniformly coated on the surface of the resist layer, and development can be performed uniformly. Since the wettability is good, the uniformity of development can be sufficiently ensured even in shower development. In dip development, even if the flow of the phenomenon liquid on the surface of the substrate to be developed is somewhat bad, the uniformity of development can be sufficiently secured. Therefore, a good resist pattern can be formed, and a product with good quality can be manufactured. Further, since the wettability is good, the consumption of the developer can be reduced. In particular, in paddle development, even if the surface of the resist layer is uneven, it is not necessary to increase the film thickness of the developer, and the consumption of the developer can be reliably reduced.

The lyophilic processing gas is preferably nitrogen gas or a mixed gas of nitrogen and oxygen. The oxygen content of the lyophilic processing gas is preferably 0 to 20% by volume, more preferably 0 to 5% by volume, and still more preferably 0.01 to 1% by volume.

The atmospheric pressure remote plasma lyophilic process is performed near atmospheric pressure including atmospheric pressure. The vicinity of atmospheric pressure means a range of 1.013 × 10 ⁴ Pa to 50.663 × 10 ⁴ Pa, and considering the ease of pressure adjustment and the simplification of the apparatus configuration, 1.333 × 10 ⁴ Pa to 10 .664 × 10 ⁴ Pa is preferable, and 9.331 × 10 ⁴ Pa to 10.9797 × 10 ⁴ Pa are more preferable.

As a lyophilic (surface wettability imparting, surface energy improvement) treatment method, ultraviolet irradiation treatment or corona treatment in an oxygen (air) atmosphere is well known. However, since the resist is photosensitive, ultraviolet irradiation treatment cannot be applied. Further, in the corona treatment, if a metal film is coated on the substrate to be processed, local arc discharge may fall on the metal film, and the substrate to be processed may be damaged.
It is conceivable that wettability is imparted by exposure to oxygen plasma under vacuum, but placing the substrate to be processed in a vacuum device, removing it after plasma processing, and proceeding to the next process will increase the process and increase equipment costs. In addition, the processing time is increased.

Even in the case of atmospheric pressure plasma lyophilic processing, in the case of atmospheric pressure direct plasma lyophilic processing in which the substrate to be processed is placed inside a discharge space near atmospheric pressure and the substrate is directly irradiated with plasma, Is difficult to adopt because it is irradiated onto the photosensitive resist. In addition, if a metal film is coated on the substrate to be processed, the metal film may be discharged, and the substrate to be processed may be damaged.

In contrast, in the atmospheric pressure remote plasma lyophilic process, the substrate to be processed is arranged away from the discharge space near the atmospheric pressure, and the processing gas converted into plasma in the discharge space is blown out toward the substrate to be processed. Therefore, by adjusting the positional relationship between the discharge space and the process gas blowout port, or by providing a light shielding member between the discharge space and the blowout port or between the blowout port and the substrate to be processed, It is possible to easily avoid the generated plasma light from hitting the substrate to be processed, and to prevent the resist from being altered by the plasma light. Even if a metal film is coated on the substrate to be processed, the distance between the electrode and the substrate to be processed is adjusted, or an electric field shielding member made of an electrically grounded conductor is provided between the electrode and the substrate to be processed. By interposing it in the substrate, it is possible to easily prevent the substrate to be processed from being damaged.

After the resist coating process and before the exposure process, an atmospheric pressure remote plasma ashing process is performed in which an ashing process gas is blown out through another discharge space in the vicinity of atmospheric pressure to contact the resist layer. preferable.
In the atmospheric pressure remote plasma ashing process, the surface layer portion of the resist layer is lightly ashed (light ashed) in the vicinity of atmospheric pressure including atmospheric pressure. The layer portion below the surface layer of the resist layer is left by adjusting the ashing time and the processing gas conditions. In remote plasma ashing, the swelled portion of the object to be processed is more likely to come into contact with the active ashing gas and the ashing speed is higher than that of the recessed portion. Thereby, the thickness of the resist layer can be made uniform, and the surface of the resist layer can be flattened. Therefore, in the subsequent exposure step, the resist portion to be exposed can be uniformly exposed and uniformly altered, and the altered resist portion and the unaltered resist portion can be clearly distinguished. Therefore, in the development process, the resist portion removed by the developer and the remaining resist portion can be clearly distinguished. As a result, a better resist pattern can be formed. Furthermore, it is possible to further reduce the consumption of the developing solution per one substrate to be processed. Particularly in paddle development, the thickness of the developer film stretched on the resist layer can be further reduced, and the consumption of the developer can be reliably reduced.

The ashing processing gas is preferably nitrogen gas or a mixed gas of nitrogen and oxygen. The oxygen content of the ashing processing gas is preferably 0 to 20% by volume, more preferably 0 to 10% by volume, and still more preferably 0.01 to 5% by volume.

Note that it is difficult to light ash the resist with vacuum plasma. This is because if the pre-baked resist is put in a vacuum apparatus and evacuated, the solvent in the resist is volatilized and the composition of the resist is altered.
Since the resist is photosensitive, it cannot be light ashed with an ultraviolet asher. The ultraviolet asher is a photoexcited ashing apparatus that strips a resist using a chemical reaction between the gas and a resist under irradiation of ultraviolet rays in an ashing chamber into which a gas such as ozone is introduced.

Even in the case of atmospheric pressure plasma ashing, in the case of atmospheric pressure direct plasma ashing in which a substrate to be processed is placed inside a discharge space near atmospheric pressure and the substrate is directly irradiated with plasma, the plasma light is exposed to a photosensitive resist. Is difficult to adopt. In addition, if a metal film is coated on the substrate to be processed, the metal film may be discharged, and the substrate to be processed may be damaged.

In contrast, in the atmospheric pressure remote plasma ashing, the substrate to be processed is arranged away from the discharge space near the atmospheric pressure, and the processing gas converted into plasma in the discharge space is blown out toward the substrate to be processed. Therefore, by adjusting the positional relationship between the discharge space and the process gas blowout port, or by providing a light shielding member between the discharge space and the blowout port or between the blowout port and the substrate to be processed, It is possible to easily avoid the generated plasma light from hitting the substrate to be processed, and to prevent the resist from being altered by the plasma light. Even if a metal film is coated on the substrate to be processed, the distance between the electrode and the substrate to be processed is adjusted, or an electric field shielding member made of an electrically grounded conductor is provided between the electrode and the substrate to be processed. By interposing it in the substrate, it is possible to easily prevent the substrate to be processed from being damaged.

A device according to the present invention is manufactured by the above-described resist pattern forming method. Examples of the device include a photoresist and a color filter. By applying the method for forming a resist pattern according to the present invention to the production of a photoresist, a photoresist having a good transfer pattern can be obtained. By using this photoresist, it is possible to manufacture an electronic device product of excellent quality. By applying the resist pattern forming method according to the present invention to the manufacture of a color filter, a color filter having a good matrix pattern and thus a good RGB pattern can be obtained.

According to the present invention, the surface of the resist layer can be made lyophilic and wettability can be improved. By performing development on that, the developer can be uniformly coated on the surface of the resist layer, and development can be performed uniformly. Thereby, a good quality resist pattern can be formed. Further, the consumption of the developer can be reduced.

1 is a cross-sectional view of a photomask blank showing a photomask (device) manufacturing process according to an embodiment of the present invention, after a resist coating process or a pre-bake process, and before an atmospheric pressure remote plasma ashing process. It is front sectional drawing which shows explanatoryally the atmospheric pressure remote plasma ashing process in the manufacturing process of the said photomask. It is front sectional drawing which shows explanatoryally the exposure process in the manufacturing process of the said photomask. It is front sectional drawing which shows explanatoryly the atmospheric pressure remote plasma lyophilic process in the manufacturing process of the said photomask. It is front sectional drawing which shows the image development process in the manufacturing process of the said photomask explanatory. It is front sectional drawing which shows explanatoryally the light shielding film etching process in the manufacturing process of the said photomask. It is sectional drawing of the said photomask.

Hereinafter, an embodiment of the present invention will be described.
As shown in FIG. 7, the device to be manufactured in this embodiment is a photomask 9. The photomask 9 has a glass substrate 91. A light shielding film 92 is coated on the surface of the glass substrate 91. A predetermined pattern 92 a is formed on the light shielding film 92.

A method for manufacturing the photomask 9 will be described.
[Washing process]
First, the surface of the glass substrate 91 is washed, and organic substances and lipids on the surface of the substrate 91 are removed. Thereby, the adhesion of the light shielding film 92 and the resist 93 can be secured.

[Shading film forming step]
Next, as shown in FIG. 1, a light shielding film 92 is coated on the entire surface of the glass substrate 91 to form a photomask blank 90. A component of the light shielding film 92 is, for example, a metal such as chromium. As the coating method, for example, sputtering is applied.

[Resist application process]
Next, a resist made of a liquid photosensitive resin is applied on the light shielding film 92 to form a resist layer 93. In this embodiment, a positive resist is used, but a negative resist may be used. The thickness of the resist layer 93 is about several μm to 100 μm. As the coating machine, a spin coater or a slit coater may be used. When the resist is applied by spin coating, the resist thickness on the outer peripheral portion of the photomask blank 90 tends to be larger than the resist thickness on the inner side of the photomask blank 90. When applied by slit coating, the resist thickness at the beginning of coating tends to be larger than at other portions. Therefore, as exaggeratedly shown in FIG. 1, the surface (upper surface) of the resist layer 93 tends to be uneven.

[Pre-baking process]
Next, the photomask blank 90 is baked and the resist layer 93 is cured.

[Atmospheric pressure remote plasma ashing process]
Next, as shown in FIG. 2, the photomask blank 90 is introduced into the atmospheric pressure remote plasma ashing apparatus 1. The atmospheric pressure remote plasma ashing apparatus 1 has a processing head 10. A pair of electrodes 11 is provided in the processing head 10 so as to face each other. A solid dielectric layer (not shown) is formed on the opposing surface of each electrode 11. One electrode 11 is connected to a power source 12. The other electrode 11 is electrically grounded. By supplying voltage from the power supply 12, the space between the

electrodes

11, 11 becomes a discharge space 13 near atmospheric pressure. The waveform of the supply voltage of the power supply 12 may be a pulse wave or a continuous wave.

The ashing processing gas supply source 14 is connected to the upstream end of the discharge space 13. As the processing gas for ashing of the supply source 14, a pure nitrogen gas or a mixed gas of nitrogen and oxygen is used. The oxygen concentration in the processing gas is preferably 0 to 20% by volume, more preferably 0 to 10% by volume, and still more preferably 0.01 to 5% by volume.

This ashing processing gas (N ₂ + O ₂ ) is introduced into the discharge space 13 to be turned into plasma. The plasma-ized processing gas is blown out from the blowout port 15 at the bottom of the processing head 10. A photomask blank 90 is disposed below the processing head 10. The photomask blank 90 is sprayed with the ashing processing gas that has been converted into plasma. As a result, the surface layer portion 93e of the resist layer 93 is lightly ashed as indicated by the phantom line in FIG. By adjusting the ashing time and the processing gas conditions, the resist layer 93 below the surface layer portion 93e is left. Usually, in the remote plasma irradiation, the raised portion of the object to be processed is closer to the processing head 10 than the recessed portion of the object to be processed, and comes into contact with a higher activity ashing gas, resulting in a higher ashing speed. large. Therefore, the convex portion on the surface of the resist layer 93 is removed by ashing prior to the concave portion on the surface of the resist layer 93. Thereby, the thickness of the resist layer 93 can be made uniform, and the surface of the resist layer 93 can be flattened. Therefore, in the resist coating process, it is not necessary to require the uniformity of coating severely.

In parallel with the blowing of the ashing process gas, the photomask blank 90 is reciprocated left and right by the moving mechanism 17. The photomask blank 90 may be fixed and the processing head 10 may be reciprocated. The speed and number of reciprocating movements are appropriately set according to the type of resist and the film thickness to be ashed, and preferably set to such an extent that the resist is lightly ashed. Specifically, the moving speed is preferably 0.2 to 10 m / min, and more preferably 0.5 to 2 m / min. The number of movements is preferably about 5 to 50 times, with one way in the forward or backward direction as one time.

Furthermore, the photomask blank 90 may be heated to an appropriate temperature by the heating unit 18.

Since the photomask blank 90 is disposed outside the discharge space 13, it is possible to easily prevent the light shielding film 92 from being damaged by being exposed to plasma. Further, the arrangement relationship between the discharge space 13 and the outlet 15 is adjusted, or a light shielding member (not shown) is provided between the discharge space 13 and the outlet 15 or between the outlet 15 and the photomask blank 90. By doing so, it is possible to easily avoid the plasma light generated in the discharge space 13 from hitting the photomask blank 90. As a result, the resist layer 93 can be prevented from being altered by the plasma light.
An electric field shielding member 16 is preferably provided at the bottom of the processing head 10. The electric field shielding member 16 is made of metal and is electrically grounded. The electric field shielding member 16 shields the electric field from the electrode 11 connected to the power source 12, and thus prevents arc discharge from dropping from the electrode 11 to the light shielding film 92. Thereby, it can prevent that the photomask blank 90 receives an electric field damage.
The smaller the distance WD between the processing head 10 and the photomask blank 90, the more effective. However, even when the photomask blank 90 is warped, the distance is set such that the processing head 10 does not contact. Usually, the distance WD is preferably WD = 0.3 to 10 mm, and more preferably 0.5 to 3 mm.

[Exposure process]
Next, as shown in FIG. 4, the photomask blank 90 is irradiated with the electron beam 3a by the electron beam irradiation apparatus 3, and the photomask blank 90 is drawn so as to draw a desired pattern at the irradiation point of the electron beam 3a. Move relative to. Thereby, the resist layer 93 can be partially exposed. Since the surface of the resist layer 93 is sufficiently flattened, the resist portion 93a to be exposed in the resist layer 93 can be uniformly exposed to be uniformly altered. Therefore, it is possible to clearly distinguish the resist portion 93a that has been altered by the exposure from the resist portion 93b that has not been exposed and has not been altered.

Instead of directly drawing a pattern with the electron beam 3a, a pattern mask may be disposed on the upper side of the photomask blank 90, and ultraviolet rays may be partially irradiated to the resist layer 93 through the pattern holes of the pattern mask 3. As ultraviolet rays, mainly 436 nm g-line or 365 nm i-line is used. Any ultraviolet ray may be selected according to the type of resist. The exposure time of ultraviolet rays is usually about several seconds to 30 seconds.

[PEB (Post Exposure Bake) process]
The photomask blank 90 after exposure is baked. This step is often omitted.

[Atmospheric pressure remote plasma lyophilic process]
Next, as shown in FIG. 4, the photomask blank 90 is introduced into the atmospheric pressure remote plasma lyophilic apparatus 2. The atmospheric pressure remote plasma lyophilic apparatus 2 has a processing head 20. A pair of

electrodes

21, 21 are provided in the processing head 20 so as to face each other. A solid dielectric layer (not shown) is formed on the opposing surface of each electrode 21. One electrode 21 is connected to a power source 22. The other electrode 21 is electrically grounded. By supplying voltage from the power supply 22, the space between the

electrodes

21 and 21 becomes a discharge space 23 near atmospheric pressure. The waveform of the supply voltage of the power supply 22 may be a pulse wave or a continuous wave.

A lyophilic processing gas supply source 24 is connected to the upstream end of the discharge space 23. As the lyophilic processing gas of the supply source 24, a pure nitrogen gas or a mixed gas of nitrogen and oxygen is used. The oxygen concentration in the processing gas is preferably 0 to 20% by volume, more preferably 0 to 5% by volume, and still more preferably 0.01 to 1% by volume.

This processing gas (N ₂ + O ₂ ) is introduced into the discharge space 23 and turned into plasma. The plasma-ized processing gas is blown out from the blowout port 25 at the bottom of the processing head 20. A photomask blank 90 is placed below the processing head 20. The plasma-processed processing gas is sprayed onto the photomask blank 90. Thereby, the surface energy of the resist layer 93 is increased, and the surface of the resist layer 93 can be made lyophilic to improve the wettability with respect to the developer.

In parallel with the spraying of the processing gas, the photomask blank 90 is moved in the left-right direction by the moving mechanism 27. The photomask blank 90 may be fixed and the processing head 20 may be moved. Although the speed and number of movements can be set as appropriate, one movement in one direction is usually sufficient.

Since the photomask blank 90 is disposed outside the discharge space 23, the light shielding film 92 can be easily prevented from being damaged by being exposed to plasma. Further, the arrangement relationship between the discharge space 23 and the outlet 25 is adjusted, or a light shielding member (not shown) is provided between the discharge space 23 and the outlet 25 or between the outlet 25 and the photomask blank 90. By doing so, it is possible to easily avoid the plasma light generated in the discharge space 23 from hitting the photomask blank 90. As a result, the resist layer 93 can be prevented from being altered by the plasma light.
An electric field shielding member 26 is preferably provided at the bottom of the processing head 20. The electric field shielding member 26 is made of metal and is electrically grounded. The electric field shielding member 26 shields the electric field from the electrode 21 connected to the power source 22, and thus prevents arc discharge from dropping from the electrode 21 to the light shielding film 92. Thereby, it can prevent that the photomask blank 90 receives an electric field damage.

[Development process]
Next, as shown in FIG. 5, the developer 5 is brought into contact with the photomask blank 90. Since the surface of the resist layer 93 is hydrophilized by the atmospheric pressure remote plasma treatment in the previous step, the developer 5 can be brought into contact with the surface of the resist layer 93 quickly and uniformly. As a result, the altered portion 93a of the positive resist layer 93 that has been irradiated with light is dissolved and removed in the developer 5, and only the unmodified portion 93b that has not been irradiated with light remains. In the case where a negative resist is used, the non-altered portion not irradiated with light is removed, and the altered portion irradiated with light remains. Since the altered portion 93a and the unmodified portion 93b are clearly separated, a desired resist pattern can be obtained.

The development method may be dip development, shower development, or paddle development. Since the developing solution 5 has good paintability, it is possible to develop sufficiently uniformly by preventing development unevenness in shower development as well as in paddle development. In the dip development, even if the flow of the phenomenon liquid on the surface of the photomask blank 90 is somewhat worse, the development uniformity can be sufficiently secured. Furthermore, since the surface of the resist layer 93 is flattened by the atmospheric pressure remote plasma ashing process before exposure, the developer 5 can be reliably brought into contact with the surface of the resist layer 93, and the development uniformity. Can be further enhanced. Furthermore, the consumption of the developer 5 per photomask blank 90 can be reduced. Particularly in paddle development, the film thickness of the developer 5 stretched on the resist layer 93 can be reduced, and the consumption of the developer 5 can be reduced. Even if the surface of the resist layer 93 is uneven, the wettability is good, so that it is not necessary to increase the film thickness of the developer 5 in paddle development, and the consumption of the developer is surely reduced. it can.

[Rinse process]
After development, wash with a rinse solution. The rinse liquid may be pure water.

[Post-baking process]
Next, after sufficiently removing the water adhering in the development process and the rinsing process, the final baking is performed to sufficiently cure the remaining resist.
The process from the cleaning process to post-baking is called a photolithography method.

[Shading film etching process]
Next, as shown in FIG. 6, the portion of the light shielding film 92 that is not covered with the resist layer 93 is etched. A portion of the light shielding film 92 covered with the resist layer 93 is left.

[Resist removal process]
Next, as shown in FIG. 7, the resist layer 93 covering the remaining light-shielding film 92 is removed by dissolving with an organic solvent or the like. Thereby, the light shielding film 92 is exposed. Since a desired resist pattern is obtained in the development process, a desired pattern 92a can be obtained for the light shielding film 92 as well. Thereby, the photomask 9 of good quality can be formed.

The present invention is not limited to the above embodiment, and various modes can be adopted within the scope of the gist.
For example, one atmospheric pressure remote plasma processing apparatus may be used as the atmospheric pressure remote plasma ashing apparatus 1 and the atmospheric pressure remote plasma lyophilic apparatus 2.
The specific procedure of each process may be changed as appropriate, and the washing process, baking process, and the like may be omitted as appropriate.
The present invention is not limited to the production of a photomask, but can also be applied to the production of other devices such as color filters by photolithography.

Examples will be described. Needless to say, the present invention is not limited to this embodiment.
A positive resist was applied to the entire surface of the glass substrate 91 by slit coating and further pre-baked. The size of the glass substrate was 510 mm × 610 mm. The initial average thickness of the resist layer 93 was 500 nm. ZEP520 manufactured by Nippon Zeon Co., Ltd. was used as the resist. The pre-baking temperature was 150 ° C.
Using the apparatus having substantially the same structure as the atmospheric pressure remote plasma processing apparatuses 1 and 2 shown in FIG. 2 or FIG. A mixed gas of nitrogen 600 L / min and oxygen 0.15 L / min was used as the processing gas. The input power from the power source 12 to the electrode 11 was 3 kW. The conveyance speed by the moving mechanism 17 was 1.2 m / min. The number of times of movement (number of times of treatment) was set to 20 times for one-way movement, and the distance between the processing head 10 and the sample was WD = 1 mm. The treatment temperature was room temperature and no heating was performed.
Thereafter, a developing process, a rinsing process, and a post-baking process were sequentially performed. The development method in the development process was dip development. ZED-50N (manufactured by Zeon Corporation) was used as a developer. The immersion time of the developer was 90 sec. Pure water was used as a rinsing liquid in the rinsing process. The post-baking temperature was 150 ° C.

Then, the thickness of the resist layer 93 was measured, and the amount of thickness reduction (initial average thickness-measured thickness) was evaluated. The measurement was performed at a total of 99 locations at intervals of 60 mm in the width direction orthogonal to the conveyance direction of the surface of the resist layer 93 and at intervals of 65 mm in the conveyance direction. Further, the water contact angle of the surface of the resist layer 93 after pre-baking (before atmospheric pressure remote plasma treatment) and after atmospheric pressure remote plasma treatment was measured.

As a comparative example, with respect to a sample subjected to the same treatment process under the same conditions as in Example 1 except that the atmospheric pressure remote plasma treatment is omitted, the resist thickness reduction evaluation and water resistance are the same as in Example 1. The contact angle was measured.

The results are shown in Tables 1 and 2 below.

As is clear from Table 1, it was confirmed that the surface of the resist layer can be planarized by performing the atmospheric pressure remote plasma treatment.
As is apparent from Table 2, the hydrophilicity of the resist layer can be greatly improved by performing the atmospheric pressure remote plasma treatment. Therefore, it was confirmed that in the subsequent development process, the developer can be brought into contact with the surface of the resist layer quickly and uniformly, and development can be performed uniformly.

The present invention is applicable to, for example, the manufacture of a photomask.

DESCRIPTION OF SYMBOLS 1 Atmospheric pressure remote plasma ashing apparatus 10 Processing head 11 Electrode 12 Power supply 13 Other discharge space 14 Processing gas supply source 15 for ashing Outlet 16 Electric field shielding member 17 Moving mechanism 18 Heating part 2 Atmospheric pressure remote plasma lyophilic apparatus 20 Processing head 21 Electrode 22 Power supply 23 Discharge space 24 Treatment gas supply source for lyophilic 25 Blowout port 26 Electric field shielding member 27 Moving mechanism 3 Electron beam irradiation machine 3a Electron beam 5 Developer 9 Photomask (device)
90 Photomask blank (object to be processed)
91 glass substrate 92 light shielding film 92a pattern 93 resist 93a altered portion 93b non-altered portion 93e ashing removal portion

Claims

A resist coating process in which a photosensitive resist is applied to the substrate of the device to form a resist layer;
An exposure step of partially irradiating the resist layer with light;
An atmospheric pressure remote plasma lyophilic process in which a processing gas for lyophilicity is blown through a discharge space near atmospheric pressure and is brought into contact with the resist layer;
A development step of bringing a developer into contact with the resist layer;
The method of forming a resist pattern characterized by sequentially executing.
2. The method of forming a resist pattern according to claim 1, wherein the lyophilic processing gas is nitrogen gas or a mixed gas of nitrogen and oxygen, and the oxygen content is 0 to 20% by volume.
A device manufactured by the method for forming a resist pattern according to claim 1.