JP5501754B2 - Method and apparatus for producing developer for photolithography - Google Patents

Description

  The present invention relates to a method and apparatus for producing a photolithography developer.

  In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, pattern miniaturization has rapidly progressed due to the advancement of photolithography technology. Such a fine pattern is achieved by miniaturizing a resist pattern formed on the surface of a substrate or the like. The resist pattern is formed by forming a resist film made of a resist composition containing a photosensitive compound on the surface of a substrate or the like, and a light, electron beam through a mask pattern in which a predetermined pattern is formed on the resist film. It is produced by performing selective exposure with an active energy ray such as a developing process. At this time, a portion of the resist film corresponding to a figure provided on the mask pattern becomes a resist pattern. Then, for example, a semiconductor element is manufactured through a process of processing the substrate by etching using this resist pattern as a mask. Among the above resist compositions, a resist composition that changes to a property in which the exposed portion dissolves in the developer is referred to as a positive type, and a resist composition that changes to a property in which the exposed portion does not dissolve in the developer is referred to as a negative type.

  In the development process of the semiconductor element manufacturing process, an alkaline aqueous solution of tetramethylammonium hydroxide (TMAH) is commonly used as the developer. TMAH is preferably used in the production of semiconductor elements because it does not contain metal ions that affect the semiconductor elements. However, when the degree of integration of semiconductor elements increases and the half pitch (HP) size becomes 49 nm or less, the swelling phenomenon that TMAH swells the resist pattern during development becomes a problem. When the resist pattern is swollen by TMAH, the rectilinearity of the resist pattern is reduced, or the resist pattern is tilted in the cleaning process after development, which causes a reduction in pattern reproducibility.

  For this reason, Non-Patent Document 1 proposes that an aqueous solution of tetrabutylammonium hydroxide (TBAH) is used as a developer instead of an aqueous solution of TMAH. By using an aqueous solution of TBAH as the developing solution, the swelling phenomenon of the resist pattern during development is alleviated, and the reproducibility of the pattern is improved.

  In addition, a developer is shipped from a developer manufacturer in a concentrated state, and the concentrated developer is diluted with pure water on the user side to prepare a developer having a predetermined concentration (for example, patent document). 1). Such a method is preferable because the developer transportation cost can be reduced.

Japanese Patent No. 2670211

The 70th JSAP Academic Lecture Presentation 2, page 635, Study of new developer for EUV resist Semiconductor Leading Edge Technologies, Julius Joseph Santillan, Toshiro Iya

  By the way, TBAH is less soluble in water than TMAH conventionally used in a developer. For this reason, when a concentrated developer containing TBAH is diluted to prepare a developer having a predetermined concentration, TBAH contained in the developer may be precipitated as crystals during the preparation. The presence of TBAH crystals in the developer may adversely affect the semiconductor element manufacturing process, which is not preferable from the viewpoint of managing semiconductor manufacturing equipment and yield of semiconductor elements. Although it is possible to remove the TBAH crystals contained in the developer with a filter, in this case, a part of the TBAH contained in the developer is removed, which causes a problem in terms of concentration management of the developer.

The present invention has been made in view of the above circumstances. When a concentrated developer containing tetrabutylammonium hydroxide (TBAH) is diluted with pure water to produce a developer having a desired TBAH concentration, method of manufacturing a photolithographic developing solution can suppress the precipitation, and an object thereof is to provide a manufacturing apparatus used in such a manufacturing method 及 beauty.

  The present inventors investigated in detail the relationship between the concentration of TBAH and the precipitation temperature of TBAH in an aqueous solution of tetrabutylammonium hydroxide (TBAH). As a result, the precipitation temperature of TBAH shows a maximum value of 27 ° C. when the concentration of TBAH is 25 to 40% by mass, and the precipitation temperature of TBAH is 27 ° C. regardless of whether the concentration of TBAH is higher or lower. Turned out to be smaller. That is, the aqueous solution of TBAH is most likely to precipitate TBAH when the amount is 25 to 40% by mass, and at this time, precipitation of TBAH is observed when the temperature of the aqueous solution is lower than 27 ° C. Although depending on the development conditions, the developer containing TBAH is usually a 6.79% by mass TBAH aqueous solution, and the concentrated developer is usually a 50% by mass or more TBAH aqueous solution. For this reason, when diluting a concentrated developer to produce a developer, the developer always passes through a state where the concentration of TBAH is 25 to 40% by mass, which is most likely to cause precipitation. That is, when the temperature of the developing solution being diluted is lower than 27 ° C., TBAH is precipitated. In other words, if the liquid temperature during dilution can always be maintained at 27 ° C. or higher, precipitation of TBAH can be suppressed. The present inventors have found the above facts and have completed the present invention.

According to a first aspect of the present invention, a first concentration of tetrabutylammonium hydroxide aqueous solution and pure water are mixed in a mixing section, whereby a second concentration of tetrahydroxide hydroxide diluted from the first concentration is used. A method for producing a photolithography developer comprising an aqueous solution containing butylammonium, wherein the temperature of the first concentration tetrabutylammonium hydroxide aqueous solution and pure water supplied to the mixing section is 27 ° C. or higher, and In the method for producing a photolithography developer, the temperature of the liquid mixed in the mixing unit is maintained at 27 ° C. or higher .

A second aspect of the present invention includes a mixing unit including a stirring unit, a first supply pipe that supplies a first concentration of tetrabutylammonium hydroxide aqueous solution, and a second supply pipe that supplies pure water. Furthermore, the first heating means for heating the tetrabutylammonium hydroxide aqueous solution supplied from the first supply pipe to the inside of the mixing section to 27 ° C. or more, and the second supply pipe to the inside of the mixing section Second heating means for heating the pure water supplied to 27 ° C. or higher, a first concentration tetrabutylammonium hydroxide aqueous solution supplied from the first supply pipe to the inside of the mixing section, and the first Pure water supplied from the two supply pipes to the inside of the mixing unit is mixed by the stirring means, and a developer for photolithography containing a second concentration of tetrabutylammonium hydroxide diluted from the first concentration is obtained. When obtaining, said mixing And thermal insulation means for maintaining the temperature at 27 ° C. or more liquids present inside which is a manufacturing apparatus for photolithography developer having a.

According to the present invention, when a concentrated developer containing tetrabutylammonium hydroxide (TBAH) is diluted with pure water to produce a developer having a desired TBAH concentration, photolithography capable of suppressing the precipitation of TBAH. mETHOD fOR pRODUCING use developer及 beauty manufacturing apparatus used in such a manufacturing method is provided.

It is a schematic block diagram which shows the manufacturing apparatus of the developing solution for photolithography used by one embodiment of the manufacturing method of this invention. It is a plot which shows the relationship between the density | concentration of TBAH in the aqueous solution of tetrabutylammonium hydroxide (TBAH), and the precipitation temperature of TBAH.

  Hereinafter, an embodiment of the method for producing a photolithography developer according to the present invention will be described. First, an example of a photolithography developer manufacturing apparatus used in the manufacturing method of this embodiment will be described with reference to FIG. FIG. 1 is a schematic configuration diagram showing an apparatus for producing a photolithography developer used in an embodiment of the production method of the present invention.

  The photolithography developer manufacturing apparatus 1 (hereinafter sometimes simply referred to as “manufacturing apparatus 1”) uses a first concentration tetrabutylammonium hydroxide (TBAH) aqueous solution, which is a concentrated developer, and pure water. Used to produce a photolithographic developer containing a second concentration of TBAH that is mixed and diluted relative to the first concentration.

  The first concentration TBAH aqueous solution is a concentrated developer containing TBAH as an alkali component. This concentrated developer is usually shipped from a developer manufacturer. The first concentration TBAH aqueous solution contains at least pure water and TBAH, and various additives may be added as necessary. Hereinafter, the first concentration TBAH aqueous solution is also simply referred to as “concentrated developer”.

  The developer for photolithography containing the second concentration of TBAH is an aqueous solution obtained by diluting the TBAH aqueous solution having the first concentration with pure water, and is a developer used in photolithography processing. That is, the manufacturing apparatus 1 is an apparatus for diluting a concentrated developer shipped from a developer manufacturer with pure water to obtain a developer used in photolithography. Hereinafter, the developer containing the second concentration of TBAH is also simply referred to as “developer”. The first concentration and the second concentration will be described later.

  The manufacturing apparatus 1 includes a mixing unit 2 for diluting the concentrated developer and a storage tank 3 for storing the developer prepared in the mixing unit 2. The mixing unit 2 includes a stirring unit 15, a first supply pipe 10 that supplies a concentrated developer to the mixing unit 2, and a second supply pipe 14 that supplies pure water to the mixing unit 2.

  The concentrated developer produced by the developer manufacturer is accommodated in a return can 31. The through can 31 can be connected to the pipe 8 from the nitrogen gas supply source 6 at the joint 7, and can be connected to the first supply pipe 10 to the mixing unit 2 at the joint 9. Here, another pipe 11 from the nitrogen gas supply source 6 is led to the bubbling tank 12 and connected to the upper part of the mixing unit 2 and the storage tank 3. Thereby, the upper space of the mixing part 2 and the storage tank 3 becomes a nitrogen gas atmosphere containing moisture. Pure water is supplied to the bubbling tank 12 from the pure water supply source 5, and the water level of the bubbling tank 12 maintains a predetermined position.

  In the middle of the first supply pipe 10 to the mixing unit 2, the sub tank 26, the filter device 13, the air valve 27, and the first heating means 51 are sequentially provided. The sub-tank 26 is provided with a liquid level sensor, and can detect that one passing can is empty. Thereby, when one passing can becomes empty, it shifts to the other passing can without delay, and the concentrated developer is continuously supplied to the first supply pipe 10. The air valve 27 is a large flow rate air valve, and a fine adjustment air valve 28 is provided in this bypass. As a result, when the concentrated developer is introduced into the mixing unit 2, the concentrated developing solution can be accurately introduced into the mixing unit 2 by using the air valve 27 to a predetermined amount and then using the air valve 28. .

  The first warming means 51 warms the concentrated developer so that the concentrated developer supplied from the first supply pipe 10 becomes 27 ° C. or higher when the concentrated developer is supplied to the mixing unit 2. The first heating unit 51 includes a heating unit such as a heater, and may further include a temperature monitoring unit for monitoring the temperature of the concentrated developer after heating. In this case, the temperature information of the concentrated developer detected by the temperature monitoring unit may be fed back to the heating unit to adjust the output of the heating unit. As the heating means, known heating means can be used without particular limitation, and an electric heater can be mentioned as an example. The temperature of the concentrated developer at the time when it is supplied to the mixing unit 2 is not particularly limited as long as it is 27 ° C. or higher, but it is preferably adjusted to 27 to 40 ° C., and adjusted to 28 to 35 ° C. More preferably.

  The second supply pipe 14 supplies pure water from the pure water supply source 5 to the mixing unit 2. In the middle of the second supply pipe 14, an air valve 29 and a second heating means 52 are provided in this order. The air valve 29 is a large flow rate air valve, and a fine adjustment air valve 30 is provided in this bypass. Thus, when pure water is introduced into the mixing unit 2, the air valve 29 is used up to a predetermined amount, and then the air valve 30 is used so that pure water can be accurately introduced into the mixing unit 2.

  The second warming means 52 warms the pure water so that the pure water supplied from the second supply pipe 14 becomes 27 ° C. or higher when the pure water is supplied to the mixing unit 2. The second heating means 52 includes a heating means such as a heater, and may further include a temperature monitoring means for monitoring the temperature of the pure water after heating. In this case, the temperature information of the pure water detected by the temperature monitoring unit may be fed back to the heating unit to adjust the output of the heating unit. As the heating means, known heating means can be used without particular limitation, and an electric heater can be mentioned as an example. The temperature of the pure water at the time when it is supplied to the mixing unit 2 is not particularly limited as long as it is 27 ° C. or higher, but is preferably adjusted to be 27 to 40 ° C., and is adjusted to be 28 to 35 ° C. It is more preferable.

  The mixing unit 2 is provided with a heat retaining means 40 including a temperature sensor 41, a heater 42, and a temperature controller 43. The heat retaining means 40 maintains the temperature of the liquid stored in the mixing unit 2 at 27 ° C. or higher. Specifically, the temperature sensor 41 detects the temperature of the liquid stored in the mixing unit 2 as temperature information, and the temperature information is sent to the temperature controller 43. Then, the temperature controller 43 adjusts the output of the heater 42 so that the temperature of the liquid accommodated in the mixing unit 2 becomes a preset temperature of 27 ° C. or higher (for example, 30 ° C.). Thereby, the temperature of the liquid accommodated in the mixing unit 2 is maintained at a temperature of 27 ° C. or higher preset in the temperature controller 43. Although the temperature of the liquid accommodated in the mixing part 2 will not be specifically limited if it is 27 degreeC or more, It is preferable to adjust so that it may become 27-40 degreeC, and it adjusts so that it may become 28-35 degreeC. Is more preferable.

  The concentrated developer and pure water supplied from the first supply pipe 10 and the second supply pipe 14 to the mixing unit 2 are uniformly stirred by the stirring means 15 to produce the developer.

  The mixing unit 2 is supported by the load cell 16, and the entire mass of the mixing unit 2 including the concentrated developer and pure water supplied therein is measured by the load cell 16.

  The mixing unit 2 and the storage tank 3 are connected by a developer supply pipe 17. The pipe 17 is provided with a pump 18 and a filter device 19 in the middle thereof, and the pipe 20 from the downstream side of the filter device 19 to the automatic analyzer 4 branches. The automatic analyzer 4 and the mixing unit 2 are connected by a return pipe 21. In addition, on the downstream side of the branch portion of the pipe 17 and on the part connecting the pipe 17 and the pipe 21, on-off valves 22 and 23 are provided.

  The upper space of the mixing unit 2, the bubbling tank 12 and the storage tank 3 is connected by a communication pipe 24 and becomes a nitrogen gas atmosphere containing moisture. Thereby, the deterioration of the developer is prevented. A pipe 25 for supplying the developer to the demand section is led out from the bottom of the storage tank 3.

  Next, a method for producing a photolithography developer in this embodiment will be described.

  First, the first concentration tetrabutylammonium hydroxide aqueous solution (concentrated developer) accommodated in the return can 31 is supplied to the mixing unit 2 via the first supply pipe 10. At this time, the concentrated developer is heated by the first heating means 51 provided in the middle of the first supply pipe 10 and is set to 27 ° C. or higher when supplied to the mixing unit 2. The concentrated developer supplied to the mixing unit 2 is kept at a temperature of 27 ° C. or higher by the heat retaining means 40 provided in the mixing unit 2. The preferable temperatures of the concentrated developer and the liquid stored in the mixing unit 2 when supplied to the mixing unit 2 are as described above.

  Next, pure water is supplied from the pure water supply source 5 to the mixing unit 2 via the second supply pipe 14. At this time, the pure water is heated by the second heating means 52 provided in the middle of the second supply pipe 14 and is set to 27 ° C. or higher when supplied to the mixing unit 2. The concentrated developer and pure water supplied to the mixing unit 2 are kept at a temperature of 27 ° C. or higher by the heat retaining means 40 provided in the mixing unit 2. The preferable temperature of pure water when supplied to the mixing unit 2 is as described above.

  Here, the reason why the temperature of the concentrated developer and pure water supplied to the mixing unit 2 and the liquid existing in the mixing unit 2 is set to 27 ° C. or higher will be described with reference to FIG. FIG. 2 is a plot showing the relationship between the concentration of TBAH and the precipitation temperature of TBAH in an aqueous solution of tetrabutylammonium hydroxide (TBAH).

  As shown in FIG. 2, when the concentration of the TBAH aqueous solution is taken on the horizontal axis and the precipitation temperature of TBAH is taken on the vertical axis, a maximum point of the precipitation temperature is observed at a location where the concentration of TBAH is 30% by mass. Here, the precipitation temperature of TBAH means a temperature at which TBAH crystals begin to precipitate in an aqueous solution of TBAH. That is, the precipitation temperature of TBAH indicates to what extent the aqueous solution of TBAH is cooled and TBAH starts to precipitate. Therefore, a high TBAH precipitation temperature means that TBAH is likely to precipitate.

  From this point of view, it can be understood that the aqueous solution of TBAH is in a state in which TBAH crystals are most likely to precipitate at 30% by mass. Here, a situation is assumed where dilution is performed with pure water from a first concentration TBAH aqueous solution as a concentrated developer to a second concentration TBAH aqueous solution used as a developer. Although depending on the development conditions, the developer containing TBAH is usually a 6.79% by mass TBAH aqueous solution, and the concentrated developer is usually a 50% by mass or more TBAH aqueous solution. Then, during the dilution from the first concentration of 50% by mass or more to the second concentration of 6.79% by mass, the TBAH is most easily precipitated. That is, as shown in FIG. 2, when the temperature of the developing solution during dilution is below 27 ° C., TBAH is precipitated when the concentration of the developing solution during dilution reaches around 30% by mass. On the contrary, if the temperature of the developing solution during dilution is maintained at 27 ° C. or higher, precipitation of TBAH can be suppressed. By adopting such a production method, the condition of passing the 30% by mass concentration at which TBAH is most likely to precipitate during dilution, that is, the concentration (first concentration) of the concentrated developer exceeds 30% by mass, And even if it is the conditions which the density | concentration (2nd density | concentration) of a developing solution becomes 30 mass% or less, a concentrated developing solution can be diluted, without producing TBAH precipitation.

As a 1st density | concentration, it exceeds 30 mass% and 80 mass% or less is preferable, 40-70 mass% is more preferable, 50-60 mass% is the most preferable.
Moreover, as a 2nd density | concentration, 0.1-20 mass% is preferable, 1-10 mass% is more preferable, 5-8 mass% is further more preferable, 6.79 mass% is the most preferable. When the second concentration is 0.1% by mass or more, good developability can be imparted to the developer, and when the second concentration is 20% by mass or less, the resist pattern is dissolved by the developer. Therefore, a good development margin can be maintained.

  In order to maintain the temperature of the developing solution during dilution at 27 ° C. or higher, at least the concentrated developer (first concentration TBAH aqueous solution) and pure water supplied to the mixing unit 2 are set to 27 ° C. or higher, and the mixing unit 2 What is necessary is just to keep the temperature of the liquid accommodated in the inside of 27 degreeC or more. For this reason, in the manufacturing method of the present embodiment, as described above, the concentrated developer and pure water supplied to the mixing unit 2 are set to 27 ° C. or higher, and the liquid contained in the mixing unit 2 is contained. Is maintained at 27 ° C. or higher.

  Next, a method for setting the concentration of the concentrated developer diluted inside the mixing unit 2 to the second concentration that is a desired concentration of the developer will be described.

  As already described, first, the concentrated developer and pure water are supplied into the mixing unit 2. At this time, the supply amounts of both are made substantially equal to the desired dilution ratio. The dilution ratio here is (first concentration) / (second concentration).

  Subsequently, the concentrated developer and pure water present inside the mixing unit 2 are uniformly mixed by the stirring unit 15, and a part of the mixed solution is sent to the automatic analyzer 4. In order to send a part of the mixed solution to the automatic analyzer 4, the valves 22 and 23 may be closed. Thereby, a part of the mixed solution is sent to the automatic analyzer 4 through the pipes 17 and 20 and the filter device 19. At this time, the insoluble matter in the mixed solution is removed by the filter device 19. If the valve 23 is opened while the inside of the mixing unit 2 is being mixed, it is convenient for removing insoluble matters existing in the mixing unit 2.

  The automatic analyzer 4 measures the TBAH concentration of the above mixed solution (diluted concentrated developer). As a measuring method, various methods such as a chemical method and a physical method can be adopted.

  In this way, the automatic analyzer 4 analyzes the concentration of TBAH in the mixed solution, and the concentration that must be added to the mixing unit 2 in order to obtain a TBAH aqueous solution (developer) having the second concentration based on this analysis value. The mass of the developer or pure water is calculated. Then, based on this calculated value, one of the concentrated developer and pure water that must be added is supplied again into the mixing section 2. Whether or not a predetermined amount of concentrated developer or pure water has been added is determined by measuring the mass of the mixing unit 2 with the load cell 16. As already described, the concentrated developer or pure water added to the mixing unit 2 is heated to 27 ° C. or higher when supplied to the mixing unit 2 by the first heating unit 51 or the second heating unit 52. It is warmed.

  When the mass of the mixing unit 2 measured by the load cell 16 increases by the mass calculated above, the supply of the concentrated developer or pure water to the mixing unit 2 is stopped, and then again in the stirring unit 15 The concentrated developer and pure water inside the mixing unit 2 are uniformly mixed, and a part of the mixed solution is sent to the automatic analyzer 4 in the same manner as described above so that the TBAH concentration in the mixed solution matches the second concentration. Make sure. After the concentration of TBAH in the mixed solution coincides with the second concentration, the valve 22 is opened, and the developer having the second concentration of TBAH is transferred to the storage tank 3 via the pipe 17, and the developer Production ends.

  As shown in FIG. 2, TBAH may be deposited depending on the temperature of the surrounding environment even at the concentration of the concentrated developer or the manufactured developer. For this reason, it is preferable to appropriately provide a heat retaining means at a location where the concentrated developer or developer passes or is stored.

The following, or a resist pattern forming method using photolithography for developer prepared from the manufacturing process of photolithography developer will be described.

A resist pattern forming method using the full O preparative lithographic developer may be, except for developing using the developer on reporting, used without particular limitation a known resist pattern forming method . As an example of such a method, a negative or positive photoresist composition is applied to the surface of a substrate such as a silicon wafer, and a light or electron beam is passed through a photomask in which a predetermined pattern is formed. There is a method in which selective exposure is performed with an active energy ray such as, followed by development.

  In applying a photoresist composition to the surface of a substrate such as a silicon wafer, any known photoresist composition can be used without any particular limitation. Such a photoresist composition is commercially available and can be easily obtained. Moreover, when apply | coating a photoresist composition to the surface of a base material, a well-known coating method can be used without being specifically limited. An example of such a coating method is a method using a spin coater.

To subjected to development processing, it is sufficient to expose the photoresist composition is selectively exposed was subjected to a developing solution of the above follow. As an example of such treatment, there are a method of immersing the substrate coated with the photoresist composition in the developer, and a method of spraying the developer onto the photoresist composition present on the surface of the substrate. By such treatment, the alkali-soluble component in the photoresist composition after selective exposure is removed, and a resist pattern is formed.

The developer described above has a smaller effect of swelling the resist pattern than conventional developers using TMAH. For this reason, according to said resist pattern formation method, even if it is a case where a half pitch size forms a finer pattern than 30-40 nm, generation | occurrence | production of the problem accompanying swelling of a resist pattern, such as a pattern collapse, is suppressed. be able to.

  While the manufacturing method and manufacturing apparatus for a photolithography developer according to the present invention have been described with reference to one embodiment, the present invention is not limited to the above embodiment, and may be changed as appropriate within the scope of the configuration of the present invention. Can be added.

  For example, in the above embodiment, the concentrated developer is heated by the first heating means 51 provided in the middle of the first supply pipe 10, but the heating means provided in the passing can 31, the sub tank 26, or the like. May be heated. In this case, it is preferable that the first supply pipe 10 or the like is appropriately provided with a heat retaining means so that the temperature of the concentrated developer is maintained at 27 ° C. or higher when supplied to the mixing unit 2. In addition, a turbidity meter or the like may be provided in the mixing unit 2, the storage tank 3, each supply pipe, and the like, and a system for monitoring the presence or absence of TBAH precipitation may be provided. Furthermore, in order to further suppress the precipitation of TBAH, the mixing unit 2 may be provided with an ultrasonic device or the like, and the storage tank 3 may be provided with a stirring means, an ultrasonic device or the like.

  Moreover, in the said embodiment, although pure water was heated by the 2nd heating means 52 provided in the middle of the 2nd supply pipe | tube 14, even if it heats at the time of supplying from a pure water supply source. Good. In this case, it is preferable to appropriately provide a heat retaining means in the second supply pipe 14 or the like so that the temperature of the pure water is maintained at 27 ° C. or higher when supplied to the mixing unit 2.

  In the above embodiment, the concentrated developer and pure water are mixed inside the mixing unit 2 having a tank shape, but may be mixed by other means. For example, a pipe through which the concentrated developer flows and a pipe through which pure water flows may be merged and mixed in the water stream. In this case, in order to mix the water flow uniformly, the stirring means is provided after the merge. Note that the stirring means in this case is not limited to a rotating body, and may be, for example, a stationary body such as a protrusion provided inside the pipe in order to make the water flow turbulent.

  Moreover, in the said embodiment, although the developing solution after preparation was transferred and stored to the storage tank 3, you may store in containers, such as a drum can.

  Moreover, in the mixing part 2, you may add additives, such as a water-soluble organic solvent, surfactant, and an inclusion compound. By adding such an additive, the precipitation temperature of TBAH can be lowered, and the precipitation of TBAH can be further suppressed.

  The water-soluble organic solvent is not particularly limited as long as it is miscible with water and causes little damage to the photoresist film. Polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; diisopropyl ether, diisobutyl ether , Ethers such as diisopentyl ether, di-n-butyl ether, di-n-pentyl ether, di-sec-butyl ether, diisopentyl ether, di-sec-pentyl ether, di-tert-amyl ether; ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, Glycol ethers such as ethylene glycol monobutyl ether; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert- Examples include alcohols such as amyl alcohol. Among these, alcohols such as isopropanol, n-butanol, isobutanol and sec-butanol are preferable from the viewpoint of sufficiently improving the solubility of TBAH while suppressing dissolution and swelling of the resist pattern during development. Illustrated. The water-soluble organic solvents can be used alone or in combination of two or more.

  The amount of the water-soluble organic solvent added to the developer is preferably 1 to 10% by mass, and more preferably 3 to 7% by mass. When the addition amount of the water-soluble organic solvent is 1% by mass or more, precipitation of TBAH in the developer can be effectively suppressed. Moreover, when the addition amount of the water-soluble organic solvent is 10% by mass or less, it is possible to reduce influences such as dissolution and swelling of the water-soluble organic solvent on the resist pattern.

  The surfactant is not particularly limited, and a conventionally known surfactant can be used. Specifically, nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used.

  The anionic surfactant is not particularly limited, and a conventionally known surfactant having an anionic group can be used. Examples of such an anionic surfactant include a surfactant having a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group as an anionic group.

  Specifically, higher fatty acids having an alkyl group having 8 to 20 carbon atoms, higher alkyl sulfates, higher alkyl sulfonic acids, higher alkyl aryl sulfonic acids, other surfactants having sulfonic acid groups, or higher alcohol phosphoric acids Examples thereof include esters or salts thereof. Here, the alkyl group possessed by the anionic surfactant may be either linear or branched, and a phenylene group or an oxygen atom may be interposed in the branched chain. Some of the hydrogen atoms may be substituted with a hydroxyl group or a carboxyl group.

  Specific examples of the higher fatty acid include dodecanoic acid, tetradecanoic acid and stearic acid. Specific examples of the higher alkyl sulfate include decyl sulfate and dodecyl sulfate. Examples of the higher alkyl sulfonic acid include decane sulfonic acid, dodecane sulfonic acid, tetradecane sulfonic acid, pentadecane sulfonic acid, and stearic acid sulfonic acid.

Specific examples of higher alkylaryl sulfonic acids include dodecylbenzene sulfonic acid and decylnaphthalene sulfonic acid.
Furthermore, examples of other surfactants having a sulfonic acid group include alkyl diphenyl ether disulfonic acids such as dodecyl diphenyl ether disulfonic acid and dialkyl sulfosuccinates such as dioctyl sulfosuccinate.
Examples of higher alcohol phosphates include palmityl phosphate, castor oil alkyl phosphate, coconut oil alkyl phosphate, and the like.

  Among the above anionic surfactants, it is preferable to use a surfactant having a sulfonic acid group. Specifically, alkylsulfonic acid, alkylbenzenesulfonic acid, olefinsulfonic acid, alkyldiphenylethersulfonic acid, alkylnaphthalenesulfonic acid. And dialkylsulfosuccinate. Among these, it is preferable to use alkylsulfonic acid, alkylbenzenesulfonic acid, alkyldiphenyl ether disulfonic acid, and dialkylsulfosuccinate. The average carbon number of the alkyl group of the alkyl sulfonic acid is preferably 9 to 21, and more preferably 12 to 18. Moreover, it is preferable that it is 6-18, and, as for the average carbon number of the alkyl group of alkylbenzenesulfonic acid, it is more preferable that it is 9-15. The average carbon number of the alkyl group of the alkyldiphenyl ether disulfonic acid is preferably 6-18, and more preferably 9-15. Furthermore, 4-12 are preferable and, as for the average carbon number of the alkyl group of dialkyl sulfosuccinate, 6-10 are more preferable. Among these, it is preferable to use alkylsulfonic acid having an alkyl group having an average carbon number of 15 and alkylbenzenesulfonic acid having an alkyl group having an average carbon number of 12.

  Examples of nonionic surfactants include polyoxyethylene alkyl ethers and acetylenic nonionic surfactants. As the nonionic surfactant, those having water solubility are desirable. The range of HLB7-17 is good. When HLB is small and water solubility is insufficient, it may be made water-soluble by mixing with other active agents.

  The addition amount of the surfactant with respect to the developer is preferably 0.01 to 10% by mass, and more preferably 0.02 to 1% by mass. Furthermore, it is most preferable that it is 0.03-0.5 mass%. When the addition amount of the surfactant is 0.01% by mass or more, precipitation of TBAH in the developer can be effectively suppressed. Moreover, when the addition amount of the surfactant is 10% by mass or less, it is possible to reduce influences such as dissolution and swelling of the surfactant on the resist pattern.

  The clathrate compound is not particularly limited, and a conventionally known water-soluble clathrate compound can be used. The compound to be an inclusion compound is dissolved in an aqueous solution by inclusion of a hydrophobic compound. For this reason, the clathrate compound clathrates TBAH having a higher hydrophobicity than TMAH conventionally used in the developer, and increases the solubility of the TBAH component in the developer. By such an action, precipitation of TBAH is suppressed.

  As such an inclusion compound, a cyclic oligosaccharide is exemplified, and among them, cyclodextrin is preferably exemplified. Cyclodextrin has a cylindrical shape whose structure is distorted in a trapezoidal shape (bucket shape), and a guest compound (TBAH) is taken into this cylindrical shape to form an inclusion compound. Cyclodextrins include α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and δ-cyclodextrin. These cyclodextrins can be used alone or in combination of two or more. Moreover, you may use crown ether as an inclusion compound.

DESCRIPTION OF SYMBOLS 1 Manufacturing apparatus of photolithography developer 2 Mixing part 10 1st supply pipe 14 2nd supply pipe 15 Stirring means 40 Thermal insulation means 51 1st heating means 52 2nd heating means

Claims (3)

Photolithography for obtaining an aqueous solution containing tetrabutylammonium hydroxide having a second concentration diluted with respect to the first concentration by mixing a tetrabutylammonium hydroxide aqueous solution having a first concentration with pure water in a mixing unit. A method for producing a developing solution for an automobile, comprising:
The temperature of the first concentration tetrabutylammonium hydroxide aqueous solution and pure water supplied to the mixing unit is 27 ° C. or higher, and the temperature of the liquid mixed in the mixing unit is maintained at 27 ° C. or higher. A method for producing a developer for photolithography.   2. The method for producing a photolithography developer according to claim 1, wherein the first concentration exceeds 30 mass% and the second concentration is 30 mass% or less. Stirring means;
A first supply pipe for supplying an aqueous solution of tetrabutylammonium hydroxide having a first concentration;
A second supply pipe for supplying pure water, and a mixing unit including
further,
First heating means for heating the tetrabutylammonium hydroxide aqueous solution supplied from the first supply pipe to the inside of the mixing section to 27 ° C. or higher;
Second heating means for heating pure water supplied from the second supply pipe to the inside of the mixing section to 27 ° C. or higher;
The first concentration tetrabutylammonium hydroxide aqueous solution supplied from the first supply pipe to the inside of the mixing section and the pure water supplied from the second supply pipe to the inside of the mixing section are mixed by the stirring means. Then, when obtaining a photolithography developer containing a second concentration of tetrabutylammonium hydroxide diluted from the first concentration, the temperature of the liquid existing inside the mixing section is maintained at 27 ° C. or higher. A lithographic developer manufacturing apparatus, comprising:

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