TWI783122B - the cleaning method - Google Patents

Abstract

The object of the present invention is to provide a cleaning method capable of preferably removing residues remaining on a substrate in a cleaning step after a developing step in photolithography. In the cleaning method, while the substrate that has completed the development step in photolithography is rotated, the nozzle that discharges the cleaning liquid is moved from the center side of the rotation of the substrate to the peripheral side to clean the substrate, and the distance between the nozzle and the substrate is The distance from the center of rotation reduces the speed of nozzle movement from the center side to the peripheral side.

Description

the cleaning method

The present invention relates to a method for cleaning a substrate after a development step when manufacturing a semiconductor device or the like by photolithography.

When manufacturing CCD (Charge Coupled Device) sensors and the like by photolithography, after developing resist materials such as color resists (color filter materials), in order to remove the developer and resist Cleaning (rinsing) of substrates such as wafers is carried out to remove residues of additive materials.

As an example of such substrate cleaning, as described in Patent Document 1, the substrate is rotated and a nozzle that discharges a cleaning liquid (rinsing liquid) is moved from the rotation center side to the peripheral edge side of the substrate. [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2014-017393

In order to improve product yield, it is important to remove residues in the cleaning step after the developing step.

For example, a developing machine used for semiconductor photoresists is used as a developing machine used when forming a color filter with a color resist. The temperature and humidity in the chamber of these developing machines, the flow rate of developing solution and cleaning solution, the rotation speed and processing time of substrates, and the movement of nozzles during developing and cleaning are strictly controlled and automated. Thereby, a plurality of semiconductor substrate products can be manufactured continuously with the same quality.

In the color resist composition, for example, the alkali-soluble portion swells with an alkaline developer, so the portion swollen with the colorant (pigment or dye) can be washed away by washing. The color resist composition contains a colorant. If the residue containing the colorant is mixed into the color resist composition of the color filter to be formed next, the color characteristics of the color filter will deteriorate due to color mixing, which will cause a decrease in yield. Therefore, in order to prevent deterioration of the color characteristics of the color filter caused by color mixing, it is necessary to reliably remove residues in the cleaning step. In this regard, it is important to obtain a cleaning ability sufficient to clean other than the portion where a pattern is to be formed by cleaning.

In recent years, substrates have been increasing in diameter (for example, 300 mm in diameter, etc.). Therefore, in the cleaning step, it is difficult to remove the residue uniformly. For large-diameter substrates, it is difficult to remove residue uniformly, especially on the peripheral side of the substrate, for example, from the peripheral portion (end) to the inner 50mm region. Among the residues on the peripheral portion of the substrate, aggregates of residues remained in stripes in many cases. Regarding the removal of development residues, in addition to the developer, the cleaning process plays a major role. In particular, in order to remove residues of compositions containing colorants such as color resists, high-pressure cleaning or the like is sometimes performed by spray cleaning, but there is a problem that it is extremely difficult to remove residues at the periphery of the substrate due to the large diameter. .

The object of the present invention is to solve the problems of the prior art, and to provide a substrate cleaning after the development step in photolithography, which can preferably remove the entire surface of the substrate including the peripheral part even if the substrate has a large diameter. The cleaning method of the resist material and developer residue on the surface.

This invention solves this problem by the following structure. [1] A cleaning method that rotates a substrate that has been subjected to a development step in photolithography, and moves a nozzle that discharges a cleaning liquid from the center side of the rotation of the substrate to the peripheral edge side to perform cleaning of the substrate with the cleaning liquid cleaning, and, The moving speed of the nozzle from the center side of the substrate's rotation center side to the peripheral edge side is decreased from the center side of the substrate's rotation center side to the peripheral edge side in accordance with the distance of the nozzle from the substrate's rotation center side. [2] The cleaning method according to item [1], wherein the rotational speed of the substrate is lowered as the nozzle moves from the rotation center side of the substrate to the peripheral side. [3] The cleaning method according to [1] or [2], wherein the decrease in the moving speed of the nozzle is at least one of linear decrease, nonlinear decrease, and stepwise decrease. [4] The cleaning method according to item [3], wherein when the decrease in the moving speed of the nozzle is at least one of a nonlinear decrease and a stepwise decrease, the moving speed of the nozzle is decreased from the center side of the rotation of the substrate to the peripheral side. the degree of reduction. [5] The cleaning method according to any one of [2] to [4], wherein the decrease in the rotation speed of the substrate is at least one of linear decrease, nonlinear decrease, and stepwise decrease. [6] The cleaning method according to item [5], wherein when the reduction in the rotation speed of the substrate is at least one of nonlinear reduction and stepwise reduction, the degree of reduction in the rotation speed of the substrate is reduced from the center side of the rotation of the substrate to the peripheral side. . [7] The cleaning method according to any one of [2] to [6], wherein the ratio of the rate of decrease in moving speed to the rate of decrease in rotational speed is 0.3 to 95, and the rate of decrease in the aforementioned moving speed refers to the The moving speed of the above nozzle is relative to the reduction rate of the moving speed of the nozzle when the nozzle is located at a distance of 1/15 of the substrate radius from the rotation center of the substrate; The rotational speed is the reduction rate of the rotational speed of the substrate with respect to the nozzle at a distance of 1/15 of the substrate radius from the rotation center of the substrate. [8] The cleaning method according to any one of [1] to [7], wherein the nozzle discharges the gas while discharging the cleaning liquid. [9] The cleaning method according to any one of [1] to [8], wherein in the developing step, a filter material that transmits light in a specific wavelength region is developed. [10] The cleaning method according to any one of [1] to [9], wherein the substrate is disc-shaped with a diameter of 200 mm or more. [Invention effect]

According to the cleaning method of the present invention, in the cleaning of the substrate after the development step in photolithography, even if the substrate has a large diameter, it is possible to preferably remove the resist material and the development of the entire surface of the substrate including the peripheral portion. liquid residue.

Hereinafter, the cleaning method of the present invention will be described in detail according to the preferred embodiments shown in the accompanying drawings.

An example of the cleaning method of the present invention is conceptually shown in FIG. 1 . The cleaning method of the present invention is a method of cleaning a substrate Z such as a wafer that has been subjected to a development step in photolithography to clean and remove residues of a developing solution and a resist material from the substrate Z. Specifically, in the cleaning method of the present invention, as shown by the arrow r in the figure, while the substrate Z is rotated, the nozzle (discharge nozzle) 12 that discharges the cleaning liquid is moved from the center side of the rotation of the substrate Z to the peripheral side. Move, thereby performing cleaning of the substrate Z that has completed the development step in photolithography. In addition, the one-dot chain line in the figure indicates the direction of the diameter of the circle drawn by the periphery of the substrate Z (hereinafter, also referred to as "peripheral part" or "end part") by the rotation of the substrate Z, and the two dot chain lines The intersection point of the lines is the rotation center of the substrate Z.

Here, in the cleaning method of the present invention, the moving speed of the nozzle 12 from the center side to the peripheral side of the rotation center of the substrate Z is decreased from the center side to the peripheral side according to the distance from the nozzle 12 to the rotation center of the substrate Z. The details will be described later, but the cleaning method of the present invention has such a structure that even when a large wafer with a diameter of 300 mm is used as the substrate Z, it is preferable to clean the entire surface of the substrate Z including the peripheral portion. The cleaning of the substrate Z after the developing step can preferably suppress residues of developing solution and resist material remaining on the substrate Z after cleaning.

In the cleaning method of the present invention, the substrate Z to be cleaned is not limited, and various known substrates such as wafers (silicon wafers) on which various devices (electronic components, etc.) are formed by photolithography can be used. Among them, it is preferable to use a disk-shaped substrate Z such as a wafer having a diameter of 200 mm or more, especially 300 mm or more, from the viewpoint that the effect of the present invention can be well realized. In addition, the substrate Z is not limited to a perfect disk shape, and may have a linear portion such as an orientation flat.

In the cleaning method of the present invention, the resist material to be developed in the developing step before cleaning, that is, the resist material (residue of the resist material) to be cleaned is not limited, and various photolithographic materials can be used. well-known resist materials used in As an example, color resist materials (color filter materials) such as red, green, blue, and black, infrared cut filter materials, infrared transmission filter materials, etc. Transparent resist materials (such as white filter pixels exemplified in JP-A-2012-137564 ) constituting transparent pixels (white filter pixels) in image sensors, cyan, yellow, and Color resist materials for magenta pixels, gray materials for light intensity adjustment, etc. Among them, from the viewpoint that the effects of the present invention can be well realized, resist materials containing colorants (pigments, dyes, etc.) such as red, green, blue, and black color resist materials and resist materials can be preferably used. A filter material that transmits light in a specific wavelength range.

In the cleaning method of the present invention, the nozzle 12 is not limited. Therefore, the nozzle 12 can be used in photolithography by using a straight nozzle that discharges the cleaning liquid to a straight plate, a nozzle that discharges the cleaning liquid in a shower, a nozzle that discharges the cleaning liquid in a spray shape, and a nozzle that discharges the cleaning liquid in a conical shape. Various well-known nozzles are cleaned for the substrate Z on which the development step has been performed. Moreover, these nozzles may be one fluid nozzle, or may be two fluid nozzles which mix and discharge gas, such as air and nitrogen.

In the illustrated example, a cleaning liquid is supplied from a first supply pipe 14 and gas is supplied from a second supply pipe 16 to the nozzle 12 . As an example of the nozzle 12, the supplied cleaning liquid and gas are mixed, and the substrate Z is cleaned by two fluids. The two fluids of the mixed cleaning liquid and gas have a high cleaning ability. Therefore, by using two fluids, the removal efficiency of resist material residues and the like can be improved, and efficient cleaning can be performed.

There is no limitation on the cleaning solution ejected from the nozzle 12. Various types of pure water, cleaning solutions with surfactants added to pure water, and commercially available cleaning solutions can be used to clean the substrates that have undergone the development step in photolithography. Various known cleaning solutions of Z. Among them, pure water is preferably used. Similarly, the gas mixed in the cleaning solution in the nozzle 12 is not limited, and various known gases mixed in the cleaning solution when cleaning the substrate Z that has undergone the development step in photolithography, such as air and nitrogen, can be used.

The mixing ratio of the cleaning liquid and the gas when the nozzle 12 discharges two fluids is not limited, as long as it depends on the type of cleaning liquid used, the type of resist material, the discharge amount of the cleaning liquid (rinsing flow rate), and the nozzle 12 The height of the cleaning solution and the temperature of the cleaning solution may be appropriately set, and it can be used under various conditions.

However, in the present invention, the discharge from the nozzle 12 that moves from the center side of the rotation of the substrate Z to the peripheral side is not limited to two fluids that mix cleaning liquid and gas. That is, the nozzle 12 may discharge only the cleaning liquid which is not mixed with the gas. In the following description, when simply referred to as "cleaning liquid", it means both the cleaning liquid that does not mix the gas and the two fluids that mix the cleaning liquid and the gas.

In the cleaning method of the present invention, the discharge amount of the cleaning liquid discharged from the nozzle 12 is not limited, and may be appropriately set according to the type of cleaning liquid used, the type of resist material, and the like. In addition, when two fluids mixed with gas are used as the cleaning liquid, the discharge amount (supply amount) of the cleaning liquid is the discharge amount of the two fluids.

As described above, in the cleaning method of the present invention, the substrate Z is cleaned by moving the nozzle 12 from the center side of the rotation of the substrate Z to the peripheral side while rotating the substrate Z. In the cleaning method of the present invention, the substrate rotation method is not limited, and various known methods for substrate rotation in photoresist developing machines and cleaning machines used in the manufacture of semiconductor devices can be used. Also, the rotation speed of the substrate Z is not limited, and may be appropriately set according to the type of cleaning solution used, the type of resist material, and the like.

In the cleaning method of the present invention, the movement of the nozzle 12 may be in a direction from the center side of the rotation of the substrate Z to the peripheral side. As an example, the nozzle 12 is conveyed linearly from the rotation center of the board|substrate Z toward the peripheral edge side. At this time, the nozzle 12 may start to move toward the peripheral side from the state where the center of the ejected cleaning liquid coincides with the rotation center of the substrate Z, or the ejected cleaning liquid may start from a position close to the rotation center of the substrate Z to the peripheral side. move.

The method of moving the nozzle 12 is not limited, and a ball screw, surrounding transmission, air drive, etc. can be used. For example, various methods for moving the nozzle are used in photoresist developing machines and cleaning machines used in the manufacture of semiconductor devices. known methods. In addition, the moving speed of the nozzle 12 is not limited. That is, in the present invention, if the following condition is satisfied, the moving speed of the nozzle 12 may be appropriately set according to the type of cleaning liquid used and the type of resist material, etc. The distance from the center of rotation varies from the center side of the rotation of the substrate Z to the peripheral side, and the moving speed of the nozzle 12 slows down from the center side to the peripheral side.

As described above, in the cleaning method of the present invention, in the cleaning of the substrate Z in which the nozzle 12 that discharges the cleaning liquid while rotating the substrate Z moves from the center side of the rotation of the substrate Z to the peripheral side, the distance between the nozzle 12 and the substrate Z The distance from the rotation center slows down the moving speed of the nozzle 12 from the rotation center side of the substrate Z to the peripheral side toward the peripheral side. The cleaning method of the present invention has such a structure that even when a large wafer having a diameter of 300 mm is used as the substrate Z, cleaning of the substrate Z after the developing step is preferably performed up to the peripheral portion. Therefore, it is possible to preferably prevent residues of developing solution and resist material from remaining on the substrate Z after cleaning. In addition, in the following description, the rotation center side, the peripheral edge side, etc. of the board|substrate are also simply referred to as the center side, the peripheral edge side, etc. of a board|substrate.

As also described in Patent Document 1, as a cleaning method after a development step in photolithography, a method is known in which a nozzle that discharges cleaning liquid is moved from the center side to the peripheral side of the substrate while rotating the substrate. In this cleaning method, the peripheral speed (moving speed at a certain position on the circumference) of the substrate is different between the center side and the peripheral side of the substrate, and the peripheral speed gradually increases as the substrate goes from the center side to the peripheral side. Therefore, there is a problem that the cleaning time for cleaning the substrate with the cleaning solution becomes shorter as it goes toward the peripheral edge of the substrate, and it is difficult to remove the development residue on the peripheral edge of the substrate. In recent years, wafers with a diameter of 300 mm have been used as substrates. However, in such large-diameter substrates, the difference in peripheral speed between the center side and the peripheral side is very large, and it is difficult to properly clean the entire surface of the substrate to remove residues. In a large-diameter substrate, as described above, it is particularly difficult to reliably remove residues on the peripheral side, for example, in a region 50 mm inside from the peripheral portion (end), and the aggregates of residues often remain in a conical shape.

In contrast, in the cleaning method of the present invention, in the cleaning of the substrate Z in which the nozzle 12 that discharges the cleaning liquid is moved from the center side of the substrate Z to the peripheral side while the substrate Z is rotated, the distance between the nozzle 12 and the substrate Z is The distance from the center of rotation reduces the moving speed of the nozzle 12 from the center side of the substrate Z to the peripheral side (outer side). That is, in the cleaning method of the present invention, the moving speed of the nozzle 12 on the peripheral edge side is lower than that on the center side of the substrate Z. As shown in FIG. In other words, in the cleaning method of the present invention, as the nozzle 12 is farther from the center of the substrate Z, the moving speed of the nozzle is lowered. The cleaning method of the present invention has such a structure, whereby the cleaning time for cleaning the substrate Z with the cleaning liquid ejected from the nozzle 12 is ensured on the peripheral side of the substrate Z, thereby enabling the cleaning to be performed on the center side and the peripheral side of the substrate Z. Uniformization of the cleaning time of the substrate Z by liquid cleaning. As a result, according to the cleaning method of the present invention, for example, even when a large-diameter wafer with a diameter of 300 mm is used as the substrate Z, it is preferable to clean the substrate Z after the development step on the entire surface including the peripheral side of the substrate Z. , so that residues of developing solution and resist material, etc., can be preferably prevented from remaining on the substrate Z after cleaning.

In the cleaning method of the present invention, as long as the moving speed of the nozzle 12 from the center side of the substrate Z to the peripheral side is reduced from the center side of the substrate Z to the peripheral side in accordance with the distance between the nozzle 12 and the rotation center of the substrate Z, it can be adopted. Various forms. Therefore, the reduction of the moving speed of the nozzle 12 from the center side of the substrate Z toward the peripheral side according to the distance of the nozzle 12 from the rotation center of the substrate Z may be a linear decrease as conceptually shown in FIG. The nonlinear reduction as conceptually shown in FIGS. 3 and 4 may also be a stepwise reduction (stepwise reduction) as conceptually shown in FIG. 5 . Alternatively, the moving speed of the nozzle 12 may be reduced from the center side to the peripheral side of the substrate Z in accordance with the distance from the nozzle 12 to the rotation center of the substrate Z, including two or more of linear reduction, nonlinear reduction, and step reduction. In the following description, "the reduction of the moving speed of the nozzle 12 from the center side of the substrate Z to the peripheral side according to the distance of the nozzle 12 from the rotation center of the substrate Z" is also simply referred to as "the reduction of the moving speed of the nozzle 12".

As shown in FIG. 2 , when decreasing the moving speed of the nozzle 12 linearly (proportionally), as an example, determine the moving speed (reference speed) as a reference, and the distance from the center of the substrate Z with the moving speed of the nozzle 12 as the reference speed. The distance (reference distance) and the degree of speed reduction (the speed reduction rate relative to the movement amount per unit distance) can be reduced according to the distance from the nozzle 12 to the center, so that the speed of the nozzle 12 can be reduced as follows: Moving speed=reference speed-(reference speed×speed reduction rate)×[(distance from nozzle to center-reference distance)/unit distance] For example, if the reference speed is set to 16.7mm/sec, the reference distance is set to 50mm, the unit distance is set to 10mm, and the speed reduction rate is set to 4% (the speed is reduced by 4% by the movement of the nozzle of 10mm), according to the nozzle 12 distance from the center and reduce the speed of movement of the nozzle 12, to become as follows: Moving speed=16.7-(16.7×0.04)×[(distance from nozzle to center-50)/10]

In addition, as shown in FIG. 3 , when the moving speed of the nozzle 12 is decreased nonlinearly, a method of decreasing the moving speed of the nozzle 12 in inverse proportion is illustrated as an example. Here, when reducing the moving speed of the nozzle 12 nonlinearly, it is preferable to change the degree (width, ratio) of speed reduction according to the distance between the nozzle 12 and the center of the substrate Z. Specifically, similar to the graph conceptually shown in FIG. 3 and when the velocity is decreased in inverse proportion, it is preferable to decrease the degree of decrease in the velocity of the nozzle 12 toward the periphery of the substrate Z. In other words, it is preferable to greatly reduce the moving speed on the center side and to reduce the reduction in moving speed on the peripheral side. For example, on the center side of the substrate Z, the moving speed of the nozzle 12 is non-linearly reduced so that the speed drops by 70% by a movement of 50 mm, and the moving speed of the nozzle 12 is non-linearly reduced on the peripheral side of the substrate Z so that by a movement of 50 mm Movement speed is reduced by 5%. This aspect is preferable in preventing excessive cleaning liquid from being discharged at the center side of the substrate Z that can be sufficiently cleaned, shortening the cleaning time of the substrate, and focusing on cleaning the peripheral portion with a lot of residue. Furthermore, the reduction of the moving speed of the non-linear nozzle 12 can also be configured by reducing the moving speed of the linear nozzles 12 with different degrees of reduction (inclination) of the combined moving speed as conceptually shown in FIG. 4 . In this case, as shown in FIG. 4 , it is preferable to increase the degree of reduction in the moving speed of the linear nozzles on the center side of the substrate Z and to decrease the degree of reduction in the moving speed of the linear nozzles on the peripheral side. Also, in the example shown in FIG. 4 , two types of reductions in the linear moving speed are combined, but three or more types of reductions in the linear moving speed may be combined instead of linearly reducing the moving speed of the nozzle 12 .

As shown in FIG. 5 , when the moving speed of the nozzle 12 is gradually reduced, the degree of reduction in the moving speed can be uniform over the entire area from the center to the peripheral edge of the substrate Z, or can be adjusted from the center to the peripheral edge of the substrate Z. The movement speed is different depending on the distance. In addition, a region where the degree of reduction in velocity is uniform and a region where the degree of decrease in velocity is not uniform may exist in mixture. Here, from the point of view that the same effect as the nonlinear speed reduction can be obtained, even when the moving speed of the nozzle 12 is gradually reduced, as conceptually shown in FIG. It is preferable to reduce the degree of decrease (ratio of change) in the velocity of the nozzle 12 as the distance goes toward the peripheral edge side of the substrate Z. Also, when the moving speed of the nozzle 12 is gradually reduced, the moving distance of the nozzle 12 at a constant speed may be uniform or non-uniform, or a mixture of uniform and non-uniform areas may exist. In addition, it is preferable to set the moving speed of the nozzle 12 to be constant so that the moving distance becomes longer as it goes toward the peripheral side.

In the cleaning method of the present invention, the moving speed of the nozzle 12 is basically lowered such that the speed on the peripheral side is lower than that on the center side. That is, in the cleaning method of the present invention, the moving speed of the nozzle 12 can be gradually reduced as shown in FIG. 5 , including a constant velocity region, basically gradually decreasing from the center side to the peripheral side. However, the present invention is not limited thereto. For example, when the processing time is to be shortened, a region where the nozzle 12 moves at a higher speed on the peripheral side than the center side may be locally provided as required. That is, in the cleaning method of the present invention, it is only necessary that the moving speed of the nozzle 12 gradually decrease from the center side to the peripheral side in the state from the center (rotation center) of the substrate Z to the peripheral portion of the substrate Z when viewed as a whole.

According to the cleaning method of the present invention, as described above, the cleaning time for cleaning the substrate Z with the cleaning liquid discharged from the nozzle 12 is ensured on the peripheral side of the substrate Z, so that the center side and the peripheral side of the substrate Z can be cleaned by the cleaning liquid. Uniformization of the cleaning time for cleaning the substrate Z. That is, according to the cleaning method of the present invention, the cleaning degree per unit area, that is, the cleaning time can be made uniform on the center side and the peripheral side of the substrate Z. In the cleaning method of the present invention, the moving speed of the nozzle 12 is reduced over the entire surface of the substrate Z so that the ratio of the maximum value and the minimum value of the cleaning time per unit area is preferably 15 times or less, more preferably 10 times. or less, more preferably 5 times or less, particularly preferably 2 times or less. In addition, the cleaning time per unit area is the time when the nozzle is located on the substrate, not the time when the cleaning liquid is in contact with the substrate Z. Also, when two fluids in which gas is mixed with the cleaning liquid are used as the cleaning liquid, the supply amount of the cleaning liquid is the supply amount of the two fluids.

Also, in the cleaning method of the present invention, the amount of the cleaning liquid ejected from the nozzle 12 can be adjusted so that the distance from the nozzle 12 to the center of the substrate Z goes closer to the peripheral portion, that is, the distance between the nozzle 12 and the center of the substrate Z The farther the distance, the more the output. In addition, in the present invention, according to the distance between the nozzle 12 and the center of the substrate Z, the pressure of the cleaning liquid discharged from the nozzle 12 can be increased as the distance goes toward the peripheral edge. At this time, the discharge amount of the cleaning liquid and/or the increase amount of the pressure may be linear like the moving speed, may be non-linear, or may be gradual. In addition, the discharge amount of the cleaning liquid and/or the degree of pressure increase may be increased toward the peripheral edge side of the substrate Z.

In the cleaning method of the present invention, in addition to the reduction of the moving speed of the nozzle 12 corresponding to the distance between the nozzle 12 and the center of the substrate Z, the distance between the nozzle 12 and the center of the substrate Z depends on the distance between the nozzle 12 and the center of the substrate Z. The farther the distance is, the lower the rotation speed of the substrate Z is better. Thereby, the cleaning time for cleaning the substrate Z with the cleaning liquid ejected from the nozzle 12 is better ensured on the peripheral side of the substrate Z, so that the cleaning of the substrate Z with the cleaning liquid can be realized on the center side and the peripheral side of the substrate Z. Time is equalized to remove development residue on the entire surface of the substrate Z including the peripheral portion.

The decrease in the rotational speed of the substrate Z according to the distance of the nozzle 12 from the center of the substrate Z may basically follow the decrease in the moving speed of the nozzle 12 described above. That is, as an example of a method of reducing the rotation speed of the substrate Z, in FIGS. 2 to 5 , it is only necessary to change the moving speed of the nozzle on the vertical axis to the rotation speed of the substrate. Therefore, the reduction of the rotational speed of the substrate Z may be linear, non-linear, or stepwise. Also, the degree of decrease in the rotational speed of the substrate Z can be reduced as the nozzle 12 goes toward the peripheral portion. When the speed is reduced stepwise, the length of the moving region of the nozzle 12 whose rotational speed is constant may be uniform or non-uniform, or a mixture of uniform and non-uniform regions may exist. In addition, the combination of the method of reducing the moving speed of the nozzle 12 (linear, nonlinear, etc.) and the method of reducing the rotation speed of the substrate Z (same as above) is not limited. Therefore, the moving speed of the nozzle 12 can be reduced linearly to reduce the rotating speed of the substrate Z linearly, the moving speed of the nozzle 12 can also be reduced linearly to reduce the rotating speed of the substrate Z, and the moving speed of the nozzle 12 can also be reduced nonlinearly to reduce the rotating speed of the substrate Z linearly. The rotation speed of the substrate Z is decreased linearly. In addition, the moving speed of the nozzle 12 may also be decreased nonlinearly to decrease the rotation speed of the substrate Z nonlinearly. Among them, it is preferable to linearly decrease the moving speed of the nozzle 12 and to nonlinearly decrease the rotation speed of the substrate Z from the viewpoint of ease of control.

Also, when reducing the moving speed of the nozzle 12 and also reducing the rotation speed of the substrate Z, it is more preferable to ensure a cleaning time for the substrate Z to be cleaned by the cleaning liquid discharged from the nozzle 12 on the peripheral side of the substrate Z, so that the substrate Z can be cleaned. The central side and the peripheral side of Z realize the uniformity of the cleaning time for cleaning the substrate Z with the cleaning liquid. That is, by reducing the moving speed of the nozzle 12, the rotation speed of the substrate Z is also reduced, whereby the degree of cleaning per unit area, that is, the cleaning time can be uniformed better on the center side and the peripheral side of the substrate Z. In the present invention, on the entire surface of the substrate Z, the moving speed of the nozzle 12 and the rotational speed of the substrate Z are reduced so that the ratio between the maximum value and the minimum value of the cleaning time per unit area becomes preferably 15 times or less, more preferably becomes 10 times or less, more preferably 5 times or less, particularly preferably 2 times or less.

In the cleaning method of the present invention, the relationship between the decrease rate of the moving speed of the nozzle 12 and the decrease rate of the rotation speed of the substrate Z is not limited. Here, in the present invention, the distance from the center (rotation center) of the substrate Z to 1/15 of the radius of the substrate Z is taken as the first reference distance, and the distance from the center of the substrate Z to the end of the substrate Z is taken as the first reference distance. The second reference distance, the decrease rate of the moving speed of the nozzle 12 and the decrease rate of the rotation speed of the substrate Z are preferably in the following relationship. For example, when the diameter of the substrate Z is 300 mm, the distance from the center of the substrate Z (rotation center) is 10 mm as the first reference distance, and the distance from the center of the substrate Z is 150 mm as the second reference distance. The movement of the nozzle 12 It is preferable that the reduction rate of the speed and the reduction rate of the rotation speed of the board|substrate Z have the following relationship. That is, the decrease rate of the moving speed of the nozzle 12 at the second reference distance (that is, the end of the substrate Z) relative to the moving speed ([mm/sec]) of the nozzle 12 at the first reference distance is the same as the position of the nozzle 12. The ratio of the decrease rate of the rotation speed of the substrate Z at the second reference distance (that is, the end of the substrate Z) to the rotation speed of the substrate Z ([rpm (revolutions per minute)]) when the nozzle 12 is located at the first reference distance is: The ratio of the reduction rate of the moving speed/the reduction rate of the rotational speed is preferably 100 or less, more preferably 50 or less, and still more preferably 10 or less. The ratio of the reduction rate of the above-mentioned moving speed/the reduction rate of the rotation speed is set to be 100 or less, thereby ensuring a cleaning time for the substrate Z to be cleaned by the cleaning liquid discharged from the nozzle 12 on the peripheral edge side of the substrate Z, thereby enabling The central side and the peripheral side of the substrate Z realize the cleaning time for cleaning the substrate Z with the cleaning liquid to remove the development residue on the entire surface of the substrate Z including the peripheral part.

Another aspect of the cleaning method of the present invention is conceptually shown in FIG. 6 . In addition, the cleaning method shown in FIG. 6 uses the same components as the cleaning method shown in FIG. 1 , so the same components are given the same symbols, and the following description will mainly describe the differences.

As described above, in the cleaning method of the present invention, the substrate Z is cleaned by moving the nozzle 12 that discharges the cleaning liquid from the center side to the peripheral side of the substrate Z while rotating the substrate Z. In addition, the cleaning of the substrate Z after the development step in photolithography is usually repeated several times. Here, in the cleaning method of the present invention, after the nozzle 12 is moved to the peripheral edge side, the cleaning liquid is not supplied to the area where the cleaning is completed, and thus unremoved residues may be dried. In particular, at the center of the substrate Z, the development residue is easily solidified. Sometimes the solidified development residue is not easy to remove, and even after repeated cleaning, it cannot be removed.

In view of this, in the present invention, as shown conceptually in FIG. At the center of the substrate Z (upper to middle stages in FIG. 6 ), cleaning liquid is discharged from the auxiliary nozzle 20 toward the center of the substrate Z, and the substrate Z is cleaned by moving the nozzle 12 from the center side to the peripheral side. The cleaning liquid discharged from the auxiliary nozzle 20 moves from the center portion of the substrate Z to the peripheral edge side due to the centrifugal force caused by the rotation of the substrate Z.

Using such an auxiliary nozzle 20 prevents the drying of the development residue, especially prevents the drying of the development residue in the central portion (near the central portion) of the substrate Z, and can preferably remove the residual development residue by the next cleaning, Accordingly, the cleaning efficiency of the substrate Z can be improved. In addition, since the development residue can also be removed by the cleaning liquid discharged from the auxiliary nozzle 20 and moved by the centrifugal force, the cleaning efficiency of the substrate Z can be improved.

The cleaning fluid discharged from the auxiliary nozzle 20 may be the same as the cleaning fluid discharged from the nozzle 12 . Therefore, the cleaning liquid ejected from the auxiliary nozzle 20 may be a cleaning liquid that does not mix gas, or may be a mixture of two fluids of cleaning liquid and gas. Here, although the cleaning ability of the two fluids of the mixed cleaning liquid and gas is high, the possibility of damaging and/or degrading the formed resist material (resist layer) and the like is also high. Since the auxiliary nozzle 20 discharges the cleaning liquid at one location, the possibility of damaging and/or deteriorating the resist material becomes higher when two fluids are used. Therefore, when the auxiliary nozzle 20 that supplies the cleaning liquid to the center of the substrate Z is used, it is preferable that the discharge product discharged from the auxiliary nozzle is the cleaning liquid of unmixed gas. In the example shown in FIG. 6, only one supply pipe 24 for supplying the cleaning liquid is provided, and the auxiliary nozzle 20 discharges the cleaning liquid without gas mixture. In addition, in the example shown in FIG. 6 , the auxiliary nozzle 20 is a single fluid nozzle (straight nozzle) that does not mix gas, but it is not limited to this as long as it can suppress damage to the resist material. In addition, depending on the shape of the nozzle, there are also nozzles of a shape that does not place the nozzle at the center. Therefore, as long as the center of the substrate Z can be filled with liquid, the auxiliary nozzle 20 does not necessarily have to be placed at the center.

The discharge amount of the cleaning liquid discharged from the auxiliary nozzle 20 is not limited, and may be appropriately set according to the type of cleaning liquid to be used, the type of resist material, and the like. Generally, it is preferable to use a flow rate of 0.01-3L (liter)/min. In addition, the method of moving the auxiliary nozzle 20 is not limited similarly to the method of moving the nozzle 12 described above, and various known methods can be employed.

In addition, in the present invention, the number of times of cleaning performed after the developing step is not limited, and may be one time, or may be repeated several times. The number of times of cleaning may be appropriately set according to the type of cleaning solution used, the type of resist material, and the like.

As mentioned above, the cleaning method of the present invention has been described in detail, but the present invention is not limited to the above examples, and it goes without saying that improvements and changes can be made within the range not departing from the gist of the present invention. [Example]

Hereinafter, specific examples of the present invention are given to describe the present invention in more detail. In addition, the present invention is not limited to the following examples.

<Example 1> [Preparation of transparent polymeric composition] The following components were mixed to prepare a transparent polymerizable composition. ・Compound having thermally polymerizable groups (manufactured by Daicel Corporation, CYCLOMER ACA-230β (CR-1000) (Mw=7700, acid value of solid content: 15 mgKOH/g) 12.191 parts by mass ・Fluorine-based surfactant (manufactured by DIC Corporation, MEGAFACE F-781) 0.834 parts by mass ・Solvent (propylene glycol monomethyl ether acetate (PGMEA)) 54.56 parts by mass ・Solvent (ethyl 3-ethoxypropionate (EEP)) 32.415 parts by mass

[Formation of clear coating layer] A coater developer (Coater Developer) (manufactured by Tokyo Electron Ltd., ACT12) provided with a heating tank having a heating plate as a heating mechanism and configured to be able to be closed was prepared. A silicon (Bare-Si) substrate with a diameter of 300 mm was prepared, and the prepared transparent polymeric composition was coated on the silicon substrate using the coating unit of a coating developer to form a coating layer with a film thickness of 0.1 μm. Thereafter, the silicon substrate was subjected to a proximity heat treatment at 220° C. for 5 minutes with a heating plate, and then cooled at 23° C. for 1 minute with a cooling plate, thereby forming a transparent coating layer.

[Preparation of green-sensing radioactive composition] The following components were mixed to prepare a green radiation-sensitive composition. ・Pigment dispersion (Green pigment dispersion G1 below) 51.2 parts by mass ・Photopolymerization initiator (BASF Corporation, IRGACURE OXE-01) 0.87 parts by mass ・Polymerizable compound (manufactured by Nippon Kayaku Co., Ltd., KAYARAD RP-1040) 4.7 parts by mass ・Adhesive (manufactured by Daicel Corporation, ACA230AA) 7.4 parts by mass ・Polymerization inhibitor (p-methoxyphenol) 0.002 parts by mass ・Additives (manufactured by TAKEMOTO OIL & FAT Co.,Ltd., Pionin D-6112-W) 0.19 parts by mass ・Silane coupling agent: (KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd., 0.9% by mass solution of cyclohexanone) 10.8 parts by mass ・Solvent (PGMEA) 14.3 parts by mass ・Solvent (cyclohexanone) 6.4 parts by mass ・Fluorine-based surfactant (4.2 parts by mass of cyclohexanone 0.2% by mass solution of MEGAFACE F-781 manufactured by DIC Corporation

(Preparation of Green Pigment Dispersion Liquid G1) A dispersant (DISPERBYK-161, 4.8 parts by mass, manufactured by BYK Chemie GmbH) and a dispersing resin (PGMEA, 83.2 parts by mass) were added to the GREEN pigment (PG36/PG7/PY139=80 parts by mass/20 parts by mass/30 parts by mass), The solid content was 25.5 mass % and the green pigment was 15.3 mass %, and the mixed liquid which mixed was prepared. In addition, PG36 is CI Pigment Green 36, PG7 is CI Pigment Green 7, and PY139 is CI Pigment Yellow 139. This liquid mixture was mixed and dispersed with a bead mill for 15 hours to prepare Green pigment dispersion liquid G1.

[Formation of green pattern] Same as above, using a coating developing machine, the substrate on which the transparent coating layer is formed is pre-baked, then transported to the coating unit, and the prepared green radiation-sensitive composition is coated on the transparent coating layer to make it become A coating layer with a film thickness of 0.6 μm. Afterwards, the substrate was subjected to proximity heating at 100° C. for 3 minutes with a heating plate, thereby drying the green radiation-sensitive composition. After drying, the substrate was cooled at 23° C. for 1 minute with a cooling plate to form a green radiation-sensitive layer.

For the thus formed green radiation-sensitive layer, use a stepper (i-ray stepper manufactured by Canon Inc., FPA5510iZs, NA/σ=0.57/0.70) at 150mJ/cm ² (exposure illuminance: 10000w/m ² ) Pattern exposure was performed at the exposure level and optimal focus setting. The exposed pattern was made into a checkered pattern with one side of the square grid being 1.0 μm, and the checkered pattern was formed in a 900×900 μm square area with the pitch of each square area set at 1000×1000 μm, and The entire surface of the substrate was exposed.

Next, the exposed substrate was loaded into a developing machine. Image development was carried out by using a developing machine manufactured by Tokyo Electron Ltd., and performing spin-on-dip image development for 60 seconds using N5 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) as a developer. A straight nozzle was used for the developing nozzle (developer flow rate: 1L/min, discharge time: 5 seconds).

Afterwards, the substrate is rotated using the rotation mechanism of the developing machine, and while the ultrapure water (DE-IONIZED WATER) at 23°C is supplied from the nozzle in a shower, the nozzle is directed from the center of the substrate (rotation center) to the periphery of the substrate in a straight line. Moving in a shape, thereby cleaning the substrate. Cleaning was performed with two fluids in which nitrogen (flow rate: 20 L/min) was mixed with ultrapure water (flow rate: 0.15 L/min). The rotation speed of the substrate was set to 1000 rpm. In addition, the movement of the nozzle was carried out as follows: with the moving speed of 16.7 mm/sec within a distance of 50 mm from the center of the substrate as the reference speed, the moving speed was reduced from the center side of the substrate to the peripheral side so as to be the same as the distance from the center of the substrate. The distance is inversely proportional. In this example, the moving speed of the nozzle within 10 mm from the center of the substrate was 83.3 mm/sec, and the moving speed of the nozzle within 150 mm from the center of the substrate was 5.55 mm/sec. The cleaning was performed by returning the nozzle to the center of the substrate again after the nozzle moved to the peripheral edge of the substrate in the first cleaning, and performing the second cleaning (two cycles were performed). After the two washes, the substrate was rotated at a rotation speed of 2000 rpm for 20 seconds to dry the substrate. As described above, a pattern in which a checkered green pattern was formed on the transparent cured layer formed on the surface of the substrate was obtained.

<Example 2> A checkered green pattern was formed on the transparent hardened layer formed on the surface of the substrate in the same manner as in Example 1, except that the moving speed of the nozzle was linearly reduced during cleaning of the substrate after development. In addition, the reduction of the moving speed of the nozzle is set as follows: with the moving speed of 16.7 mm/sec within a distance of 50 mm from the center of the substrate as the reference speed, the moving speed of the nozzle is reduced by 4% by moving the nozzle of 10 mm, and the moving speed is reduced from the center of the substrate to 16.7 mm/sec. The central side descends linearly toward the peripheral side. In this example, the moving speed of the nozzle within 10 mm from the center of the substrate was 19.3 mm/sec, and similarly, the moving speed of the nozzle within 150 mm from the center of the substrate was 10.0 mm/sec.

<Example 3> A checkered green pattern was formed on the transparent hardened layer formed on the surface of the substrate in the same manner as in Example 1, except that the moving speed of the nozzle was linearly reduced during cleaning of the substrate after development. In addition, the reduction of the moving speed of the nozzle is set as follows: with the moving speed of 16.7 mm/sec within a distance of 50 mm from the center of the substrate as the reference speed, the moving speed of the nozzle is reduced by 2% by moving the nozzle of 10 mm, and the moving speed is reduced from the center of the substrate to 16.7 mm/sec. The central side descends linearly toward the peripheral side. In this example, the moving speed of the nozzle within 10 mm from the center of the substrate was 18.0 mm/sec, and similarly, the moving speed of the nozzle within 150 mm from the center of the substrate was 13.3 mm/sec.

<Example 4> In the same manner as in Example 1, except that the moving speed of the nozzle was lowered stepwise during the cleaning of the substrate after development, a pattern in which a checkered green pattern was formed on the transparent hardened layer formed on the surface of the substrate was formed. . In addition, in reducing the moving speed of the nozzle, the following operations were repeated: the moving speed of the nozzle was kept at a constant speed while the nozzle moved 10 mm, and the moving speed was decreased by 4% after the nozzle moved 10 mm.

<Example 5> In the cleaning of the substrate after development, except that the rotation speed of the substrate was not set at a constant 1000rpm, but the rotation speed of the substrate was reduced according to the distance from the center of the substrate, the same method as in Example 1 was formed on the surface of the substrate. A green checkered pattern is formed on the transparent hardened layer. In decreasing the rotation speed of the substrate, the rotation speed was decreased in inverse proportion to the distance from the nozzle to the center of the substrate so that the rotation speed of the nozzle was 1000 rpm when the nozzle was located at a distance of 50 mm from the center of the substrate. In this example, the rotational speed of the substrate is 5000 rpm when the distance between the nozzle and the center of the substrate is 10 mm, and the rotational speed of the substrate is 333 rpm when the distance between the nozzle and the center of the substrate is 150 mm. Therefore, in this example, the diameter of the substrate is 300 mm, so a distance of 150 mm (second reference distance = end of the substrate) relative to a distance of 10 mm from the center of the substrate (first reference distance = 1/15 of the radius of the substrate) The reduction rate of the moving speed of the nozzle (83.3mm/sec and 5.55mm/sec) in the part) is 93.3%, compared to the distance between the nozzle and the center of the substrate of 10mm (the first reference distance) at a distance of 150mm (No. 2 reference distance), the reduction rate of the rotation speed of the substrate was 93.3%, and the ratio of the reduction rate of the moving speed/the reduction rate of the rotation speed was 1.00.

<Example 6> Except that when the nozzle moves from the center of the substrate, an auxiliary nozzle is provided near the center to discharge the cleaning liquid from the auxiliary nozzle, and the transparent hardened layer formed on the surface of the substrate is formed in the same manner as in Example 5. The pattern is made of the green pattern of the pattern. In addition, the cleaning liquid discharged from the auxiliary nozzle was ultrapure water not mixed with air. The flow rate of ultrapure water was set at 0.3 L/min. Also, in the final stage of cleaning (before drying), a cleaning step was added in which only the cleaning liquid was discharged from the auxiliary nozzle and cleaned at 500 rpm for 10 seconds. Nozzles (2 fluid nozzles) are installed near the center, and in the initial stage of cleaning where the auxiliary nozzle cannot be installed near the center, the auxiliary nozzle is set so that it does not discharge liquid and is retracted to the side of the nozzle. The setting is such that after the nozzle starts to move from the vicinity of the center to the peripheral portion and the auxiliary nozzle can be installed near the center, the auxiliary nozzle is moved to the vicinity of the center to discharge the cleaning liquid. In addition, the vicinity of the center is defined as a range in which the liquid discharged to the center of the substrate can cover the center of the substrate when the liquid is discharged from the auxiliary rinse nozzle to the rotating substrate.

＜Comparative example 1＞ A checkered green pattern was formed on the transparent hardened layer formed on the surface of the substrate in the same manner as in Example 1 except that the movement of the nozzle was set at a constant 16.7 mm/sec.

＜Evaluation＞ The upper surface of the checkered green pattern produced in this way was observed using a length-measuring scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, S-9380, Mag: ×30.0k, HV/IP: 600v/8.0pA) . During observation, the center of the substrate, the position at a distance of 75 mm from the center, and the peripheral portion of the substrate (at a position at a distance of 5 mm from the peripheral portion) were observed. The evaluation criteria are as follows: If there are so many residues that cannot be applied to the grade of the product grade, the evaluation is D; Although there are many residues, the grade that can be applied to the product is evaluated as C; There are few residues, and the rating is B when it is suitable for the product and there is no problem; The case where the residue was almost eliminated and the appearance was good was rated as A. The results are shown in the following tables.

<Example 7> Except having changed the board|substrate into the silicon board|substrate of diameter 200mm, it carried out similarly to Example 6, and formed the pattern which formed the green pattern of checkered pattern on the transparent cured layer formed in the surface of a board|substrate. Among them, ACT8 manufactured by Tokyo Electron Ltd. was used for coating and image development of the composition. Also, exposure was performed at an exposure amount of 145 mJ/cm ² (exposure illuminance: 10000 w/m ² ) using FPA3000i5 (NA/σ=0.63/0.65) manufactured by Canon Inc. . The upper surface of the checkered pattern green pattern produced in this way was observed similarly to the said example, and it evaluated similarly. Among them, S-9260A (Mag: ×30.0k, HV/IP: 600v/8.0pA) manufactured by Hitachi High-Technologies Corporation was used as the length-measuring scanning electron microscope. The results are collectively described in the following tables.

僅實施例7中，基板的直徑為200mm，其他例中基板的直徑為300mm 如上述表所示，根據依據距基板的中心的距離而從中心側向周緣側降低噴嘴的移動速度之本發明，與噴嘴的移動速度恆定的以往（比較例）的清洗方法相比，能夠大幅減少基板的清洗後的顯影殘渣。 尤其，與噴嘴的速度一同，依據噴嘴向周緣側移動而降低基板Z的轉速之實施例5中，幾乎確認不到基板的中心部及距中心的距離在75mm的位置之顯影殘渣，能夠較佳地進行基板的清洗。其中，尤其噴嘴從中心移動之後，藉由輔助噴嘴向中心吐出清洗液之實施例6及實施例7，在整個基板中幾乎確認不到顯影殘渣，從而進一步較佳地進行基板的清洗。 藉由以上結果證實了本發明的效果。 [產業上之可利用性][Table 1]

Only in Example 7, the diameter of the substrate is 200 mm, and the diameter of the substrate in the other examples is 300 mm. As shown in the above table, according to the present invention that reduces the moving speed of the nozzle from the center side to the peripheral side according to the distance from the center of the substrate, Compared with the conventional (comparative example) cleaning method in which the moving speed of the nozzle is constant, the development residue after cleaning the substrate can be significantly reduced. In particular, in Example 5 in which the rotational speed of the substrate Z was reduced by moving the nozzle to the peripheral side along with the speed of the nozzle, almost no development residue was observed at the center of the substrate and at a position at a distance of 75 mm from the center, which was preferable. to clean the substrate. Among them, especially in Examples 6 and 7 in which the cleaning solution was discharged from the auxiliary nozzle to the center after the nozzle moved from the center, almost no development residue was confirmed on the entire substrate, and the substrate was cleaned more preferably. The effects of the present invention were confirmed by the above results. [Industrial availability]

It can be preferably used in the manufacture of semiconductor devices using photolithography.

12‧‧‧Nozzle 14‧‧‧1st supply pipe 16‧‧‧The second supply pipe 20‧‧‧Auxiliary nozzle 24‧‧‧Supply pipe Z‧‧‧substrate r‧‧‧rotation direction

FIG. 1 is a conceptual diagram for explaining an example of the cleaning method of the present invention. Fig. 2 is a graph for explaining an example of the movement of the nozzle in the cleaning method of the present invention. Fig. 3 is a graph for explaining another example of nozzle movement in the cleaning method of the present invention. Fig. 4 is a graph for explaining another example of nozzle movement in the cleaning method of the present invention. Fig. 5 is a graph for explaining another example of nozzle movement in the cleaning method of the present invention. Fig. 6 is a conceptual diagram illustrating another example of the cleaning method of the present invention.

12‧‧‧Nozzle

14‧‧‧1st supply pipe

16‧‧‧The second supply pipe

Z‧‧‧substrate

r‧‧‧rotation direction

Claims (9)

A cleaning method, characterized in that, while rotating a substrate that has completed a development step in photolithography, a nozzle that discharges a cleaning liquid is moved from the center side of the substrate to the peripheral side of the rotation, so that the cleaning liquid cleaning the substrate, and according to the distance between the nozzle and the rotation center of the substrate, the moving speed of the nozzle is reduced from the center side to the peripheral side, and the nozzle moves from the center side to the peripheral side, then The more the rotation speed of the substrate is reduced. The cleaning method described in claim 1, wherein the reduction of the moving speed of the nozzle is at least one of linear reduction, non-linear reduction and stepwise reduction. The cleaning method described in item 2 of the scope of the patent application, wherein when the reduction of the moving speed of the nozzle is at least one of non-linear reduction and stepwise reduction, the moving speed of the nozzle is reduced from the center side to the peripheral side reduce the degree. The cleaning method described in claim 1, wherein the decrease in the rotational speed of the substrate is at least one of linear decrease, non-linear decrease and stepwise decrease. The cleaning method described in claim 4 of the patent application, wherein when the decrease in the rotational speed of the substrate is at least one of a nonlinear decrease and a stepwise decrease, the degree of decrease in the rotational speed of the substrate is reduced from the center side to the peripheral side . The cleaning method described in item 1 of the scope of the patent application, wherein the ratio of the reduction rate of the moving speed/the reduction rate of the rotational speed is 0.3~95, Wherein, the reduction rate of the moving speed refers to the moving speed of the nozzle on the periphery of the substrate relative to the moving speed of the nozzle when the nozzle is located at a distance of 1/15 of the radius of the substrate from the rotation center of the substrate The reduction rate of the rotation speed; the reduction rate of the rotation speed refers to the rotation speed of the substrate when the nozzle is located at the periphery of the substrate relative to the substrate when the nozzle is located at a distance of 1/15 of the radius of the substrate from the rotation center of the substrate The reduction rate of the rotational speed. The cleaning method described in claim 1, wherein the nozzle discharges gas while discharging the cleaning liquid. The cleaning method described in claim 1 of the patent application, wherein the substrate developed in the developing step is a filter material that transmits light in a specific wavelength region. The cleaning method described in claim 1, wherein the substrate is in the shape of a disk with a diameter of 200mm or more.

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