JP2007256710A - Washing fluid for lithography, washing method for base using the same, and washing method for chemical fluid supply device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a washing liquid for lithograph: having basic characteristics, as a washing fluid for lithography, of flexibility such that materials for forming various coatings used for a lithography stage and different uses of cleaning of a plurality of objects to be washed are exhaustively covered, washing capability of washing and removing objects to be washed efficiently in a short time, drying performance for short-time speedy drying, and further no adverse influence of the shape of a remaining film used for subsequent stages; having safety such as no adverse influence on environments and human bodies and a low flashing point; and having various demanded characteristics of being inexpensive and stably supplied. <P>SOLUTION: The washing fluid for lithography containing (A) a glycol-based organic solvent, (B) a lactone-based organic solvent, and (C) at least one kind of organic solvent selected from alkokxy benzene and aromatic alcohols is used. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a cleaning liquid used when a resist pattern is manufactured by a lithography method, and particularly to a lithography cleaning liquid suitable for manufacturing a resist pattern using an immersion lithography method.

  A semiconductor element is generally manufactured through a step of forming a photoresist pattern on a substrate by a lithography method. Recently, with the further miniaturization of semiconductor elements, liquid immersion lithography (Liquid Immersion Lithography) has been reported. In this method, at the time of exposure, an immersion medium having a predetermined thickness is disposed on at least the film to be exposed in an exposure optical path between an exposure apparatus (lens) and the film to be exposed on the substrate. It exposes and forms a resist pattern. In this immersion lithography method, an exposure optical path space, which has conventionally been an inert gas such as air or nitrogen, has a refractive index that is larger than the refractive index of these spaces (gas) and smaller than the refractive index of the resist film ( By substituting with an immersion medium having n), high resolution can be obtained even when a light source having the same exposure wavelength is used, as in the case of using exposure light having a shorter wavelength or using a high NA lens. In addition to being achieved, there are advantages such as no reduction in the depth of focus. By using such immersion lithography, it is possible to realize a resist pattern that is low in cost, excellent in high resolution, and excellent in depth of focus by using a lens mounted on an existing exposure apparatus. Has attracted a lot of attention

  In such a lithography method, a resist film corresponding to each exposure wavelength such as g-line, i-line, KrF excimer laser, ArF excimer laser, EUV, an antireflection film provided under these resist layers, and an upper layer of these resists A resist pattern is formed by using a protective film provided on the substrate.

  Further, in the resist pattern forming step in the lithography method, a step of removing an unnecessary coating film adhering to the back surface portion or the edge portion or both of the substrate after the coating film is formed on the substrate, and a coating method on the substrate. A plurality of cleaning steps are required, such as a step of removing the entire coating film existing on the base material after the film is formed, and a step of cleaning the base material before applying the coating material.

  Furthermore, the contaminants adhering to the device for supplying the materials for forming the various coating films described above to the base material adversely affect the formation of the resist pattern and the subsequent subsequent processes. On the other hand, it is necessary to perform a timely cleaning treatment.

  Moreover, the lithography cleaning liquid supply pipes installed in the semiconductor production line have a limited number of pipes, so they cover all the materials used to form various coating films and different cleaning applications for multiple cleaning targets. The versatility that it can be covered is required.

  Furthermore, as a cleaning liquid for lithography, a cleaning performance that can efficiently clean and remove an object to be cleaned in a short time, a drying performance that can be quickly dried in a short time, and a residual film used in subsequent subsequent processes. Basic characteristics such as not adversely affecting the shape are also required.

  In addition to the above versatility and basic characteristics, there are also requirements such as safety such as a low flash point without adversely affecting the environment and the human body, low cost, and stable supply.

  Conventional lithography cleaning liquids that have been used in conventional lithography methods include, for example, those composed of ethylene glycol or ester solvents thereof (see Patent Document 1), and those composed of propylene glycol alkyl ether acetate (see Patent Document 2). ), An alkyl 3-alkoxypropionate (see Patent Document 3), an alkyl pyruvate (see Patent Document 4), and the like.

Moreover, the thing using the mixture of two or more types of solvents is also known, for example, the thing using the mixture of propylene glycol alkyl ether, C1-C7 monoketone, and lactam or lactone (refer patent document 5). ), and the mixing weight ratio _x i component i, when the solubility parameter calculated was [delta] _i by Fedors method, cleaning solution for lithography composed of n type of the solvent that satisfies _{9 ≦ Σx i δ i ≦ 12} ( Patent Document 6 And a mixture using a mixture of an aceto ester, γ-butyrolactone, and a non-aceto ester (Patent Document 7) is known.

  Furthermore, a stripping solution (Patent Document 8) containing a solvent in which one or more high-boiling organic solvents having a boiling point of 120 ° C. or higher and one or more low-boiling organic solvents having a boiling point of 90 ° C. or lower is disclosed. Yes.

  However, these lithography cleaning liquids lack generality such as having a good cleaning performance only for a specific coating film, or the basic characteristics of the cleaning performance or drying performance are insufficient, and the yield is deteriorated. Or, there are some problems, such as being unable to be used for different cleaning applications of a plurality of objects to be cleaned, and not satisfying all the required performance described above.

Japanese Patent Publication No. 5-75110 Japanese Patent Publication No. 4-49938 Japanese Patent Laid-Open No. 4-42523 Japanese Patent Laid-Open No. 4-130715 Japanese Patent Laid-Open No. 11-218933 JP 2003-114538 A JP 2003-195529 A JP-A-2005-286208

  The present invention has been made in view of the above circumstances, and in particular, comprehensively covers materials for forming various coating films and different cleaning uses for a plurality of cleaning targets, which could not be achieved with conventional cleaning liquids for lithography. It has versatility that it can be covered, and can clean and remove the object to be cleaned efficiently in a short time, drying performance that dries quickly in a short time, and the remaining film used in subsequent subsequent processes It has the basic characteristics of a lithographic cleaning solution that does not adversely affect the shape of the material, and also has safety such as a low flash point without adversely affecting the environment and the human body. The present invention has been made for the purpose of providing a cleaning liquid for lithography having various required properties, such as being possible.

  The present invention provides a cleaning liquid for lithography containing (A) a glycol organic solvent, (B) a lactone organic solvent, and (C) at least one organic solvent selected from alkoxybenzene and aromatic alcohol. .

  The present invention also provides a method for cleaning a substrate, wherein the substrate is cleaned using the lithography cleaning liquid in a cleaning step in manufacturing a substrate using an immersion lithography method.

  Furthermore, the present invention provides a method for cleaning a chemical solution supply apparatus, in which a chemical solution supply apparatus for forming a coating film is cleaned using the lithography cleaning liquid in the production of a substrate using an immersion lithography method.

  The cleaning liquid for lithography of the present invention contains (A) a glycol organic solvent, (B) a lactone organic solvent, and (C) at least one organic solvent selected from alkoxybenzene and aromatic alcohol. And

As the glycol organic solvent of the component (A),
R ₁ O— (R ₂ O) _n —R ₃ (1)
(Wherein R ₁ is an alkyl group or cycloalkyl group having 1 to 6 carbon atoms, R ₂ is an alkylene group having 2 to 4 carbon atoms, R ₃ is hydrogen or an alkyl group or cycloalkyl group having 1 to 6 carbon atoms, n represents an integer of 1 to 4).

  Specific examples of the alkyl group or cycloalkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group and the like. .

  Specific examples of such glycol-based organic solvents include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol and tripropylene glycol monoalkyl ether, dialkyl ether, monocycloalkyl ether, cycloalkylalkyl diether. Is mentioned. Of these, propylene glycol monomethyl ether is preferred.

  The blending amount of the component (A) is preferably 3 to 60% by mass, and particularly preferably 5 to 50% by mass with respect to the total amount of the cleaning liquid for lithography. By setting it as such a compounding quantity, it can be set as the washing | cleaning liquid which can give the outstanding washing | cleaning performance in various washing | cleaning object and various washing | cleaning processes, and is excellent also in a drying performance.

  Examples of the lactone organic solvent of the component (B) include γ-butyrolactone, γ-valerolactone, and δ-valerolactone. Among them, γ-butyrolactone is particularly suitable because it is versatile and has excellent cleaning performance.

  The blending amount of the component (B) is preferably 3 to 40% by mass, and particularly preferably 5 to 35% by mass with respect to the total amount of the cleaning liquid for lithography. By setting it as such a compounding quantity, the outstanding cleaning performance can be given in various washing | cleaning objects and various washing processes.

  As the component (C), at least one organic solvent selected from alkoxybenzene and aromatic alcohol is used.

  Examples of the alkoxybenzene include anisole, phenetole, phenoxyethylene, methoxytoluene, pyrocatechol monomethyl ether, pyrocatechol dimethyl ether, m-methoxyphenol, m-dimethoxybenzene, p-dimethoxybenzene, vinylanisole, p- (1-propenyl). Anisole, p-allyl anisole, etc. are mentioned.

  Examples of the aromatic alcohol include benzyl alcohol, methylbenzyl alcohol, p-isopropylbenzyl alcohol, 1-phenylethanol, phenethyl alcohol, 1-phenyl-1-propanol, cinnamyl alcohol, xylene-α, α ′ diol, and salicyl alcohol. , P-hydroxybenzyl alcohol, anisyl alcohol, aminobenzyl alcohol and the like.

  Among such components (C), alkoxybenzene is particularly preferable, and anisole is particularly preferable because it is easy to handle and has excellent cleaning performance.

  The blending amount of the component (C) is preferably 20 to 80% by mass, and particularly preferably 30 to 60% by mass with respect to the total amount of the cleaning liquid for lithography. By setting it as such a compounding quantity, it can be set as the washing | cleaning liquid which can give the outstanding washing | cleaning performance in various washing | cleaning object and various washing | cleaning processes, and is excellent also in a drying performance.

  Further, a substrate cleaning method and a chemical solution supplying device cleaning method using the lithography cleaning liquid will be described below.

  The above-described cleaning liquid for lithography according to the present invention includes (I) a step of removing an unnecessary coating film that has adhered to the substrate back surface and / or the edge portion after the coating film is formed on the substrate, and (II) the substrate. Various substrate cleaning processes such as the removal process of the entire coating film existing on the substrate after forming the coating film, (III) the substrate cleaning process before applying the coating liquid for coating film formation, and (IV ) It can be applied to a plurality of cleaning applications such as a cleaning process of a chemical solution supply device for forming various coating films, and all exhibit high cleaning performance.

  The step of removing the unnecessary coating film adhering to the substrate rear surface portion and / or the edge portion after the coating film is formed on the base material (I) is specifically as follows.

  When a coating film such as a resist, an antireflection film, or a protective film is formed on the substrate, the coating film is formed on the substrate by, for example, a spin coating method using a spinner. When a coating film is applied on the substrate in this way, the coating film is diffused and applied in the radial direction by centrifugal force, so that the film thickness at the edge of the substrate is thicker than the central part of the substrate. The coating also wraps around and adheres to the back of the film.

  Then, the unnecessary coating film adhering to at least a part of the edge portion and the back surface portion of the base material is cleaned and removed by bringing the cleaning liquid for lithography of the present invention into contact therewith. By using the cleaning liquid for lithography of the present invention, it is possible to efficiently remove an unnecessary coating film on at least a part of the edge portion and the back surface portion of the substrate efficiently and in a short time. In addition, in the conventional lithography method, it was necessary to make the edge shape of the coating film into a rectangular shape in order not to adversely affect the subsequent process. However, in the immersion lithography method currently being studied, When the immersion exposure method is used, it is proposed that the cross-sectional shape be the shape shown in FIG. 1 or 2, and when the lithography cleaning liquid of the present invention is used, such a shape can be obtained. Is possible.

  The method for removing the unnecessary coating film by bringing it into contact with the cleaning liquid for lithography of the present invention is not particularly limited, and a known method can be used.

  As such a method, for example, there is a method in which the cleaning liquid is dropped or sprayed on the edge portion or the back surface portion with the cleaning liquid supply nozzle while rotating the substrate. In this case, the supply amount of the cleaning liquid from the nozzle is appropriately selected depending on the type and thickness of the coating film such as a resist to be used, but is usually selected in the range of 3 to 50 ml / min. Or the method of immersing the edge part of a base material for the predetermined time in the washing | cleaning liquid in a storage part after inserting the edge part of a base material into the storage part previously filled with the washing | cleaning liquid from the horizontal direction etc. is also mentioned. However, it is not limited to these exemplary methods.

  The removal process of the whole coating film existing on the base material after the coating film is formed on the base material (II) is specifically as follows.

  The coating film applied on the substrate is cured by heating and drying, but in the actual work process, such as when a defect occurs in the formation of the coating film, the defect does not continue without continuing the subsequent processing steps. In this process, the entire coated film is once removed by being brought into contact with the lithography cleaning liquid of the present invention. Even in such a case, the cleaning liquid for lithography of the present invention can be used. Such a process is usually referred to as a rework process, and the method of such a rework process is not particularly limited, and a known method can be used.

  Specifically, the base material washing step before applying the above-mentioned (III) coating film forming material is as follows.

  Before forming a coating film with respect to a base material, it carries out by dripping the washing | cleaning liquid for lithography of this invention on a base material. Such a process is called a pre-wet process, and this pre-wet process is also a process for reducing the amount of resist used, but in the present invention, this is one of the substrate cleaning processes. explain. Such a prewetting method is not particularly limited, and a known method can be used.

  The (IV) cleaning process of the chemical solution supply apparatus for forming various coating films is specifically as follows.

  The chemical solution supply device for forming the various coating films described above is composed of a pipe, a chemical solution application nozzle, a coater cup, etc., and by using the cleaning liquid for lithography of the present invention, the chemical solution adhered to such a chemical solution supply device and solidified. It can also be used effectively for cleaning and removal.

  As a method for cleaning the pipe, for example, the chemical liquid is completely drained from the pipe of the chemical liquid supply apparatus to be emptied, and the cleaning liquid for lithography of the present invention is poured into the pipe to fill the pipe and left as it is for a predetermined time. After a predetermined time, while the lithography cleaning liquid is being discharged from the pipe, or after being discharged, the chemical liquid for forming the coating film is poured into the pipe and passed, and then the supply of the chemical liquid onto the substrate is started.

  The cleaning liquid for lithography of the present invention can be widely applied to piping through which materials for forming various coating films are passed, has excellent compatibility, and has no reactivity. There are no abnormalities in the liquid properties such as separation and white turbidity, and there are excellent effects such as no increase in foreign matter in the liquid.

  In particular, even when chemical residues are attached to the piping due to long-term use, according to the lithography cleaning liquid of the present invention, these residues are dissolved and the cause of particle generation can be completely removed. it can. Further, when the chemical solution supply operation is resumed, the chemical solution supply operation can be started only by performing an air flow while discharging the cleaning solution or after discharging the cleaning solution.

  Further, as a cleaning method for the chemical solution application nozzle, in addition to contacting the coating film residue adhering to the application nozzle portion of the chemical solution supply device with the cleaning solution for lithography of the present invention by a known method, the attached chemical solution is washed and removed. When the application nozzle is not used for a long time, the tip of the application nozzle is dispensed in a solvent atmosphere. The cleaning liquid for lithography according to the present invention is also useful as this dispense liquid. However, it is not limited to these methods.

  Further, as a method of cleaning the coater cup, the attached chemical solution is washed and removed by bringing the coating film residue attached in the coater cup in the chemical solution supply device into contact with the cleaning solution for lithography of the present invention by a known method. be able to. However, it is not limited to such a method.

  In addition, as a coating film to be removed using the cleaning liquid for lithography of the present invention, a resist film corresponding to each exposure wavelength such as g-line, i-line, KrF excimer laser, ArF excimer laser, EUV, and the resist underlayer Examples thereof include an antireflection film provided, and a protective film provided on a resist upper layer. A well-known thing is used as such a coating film. Particularly in the immersion lithography method, it is a great merit that an antireflection film, a resist film, and a protective film are sequentially laminated on a substrate, and that the same lithography cleaning liquid can be used for all these material systems. It is.

  The resist film is made of a material containing a novolac resin, a styrene resin, an acrylic resin or the like as a base resin component, and the antireflection film provided under the resist film is a light-absorbing material. A material having a structure including an acrylic resin having a substituent of the above, and further, as a protective film provided on the upper layer of the resist film, a material including an alkali-soluble resin made of a fluorine atom-containing polymer is generally used. It is used for.

  Furthermore, in the cleaning process using the lithography cleaning liquid of the present invention, a cleaning performance that can efficiently clean the object to be cleaned in a short time is required. The time required for the cleaning process varies in various cleaning processes, but normally, the performance required to achieve cleaning in 1 to 60 seconds is required.

  Similarly, the drying performance is required to dry in a short time, but this is usually required to dry in 5 to 60 seconds.

  Furthermore, basic characteristics such as not adversely affecting the shape of the remaining film used in the subsequent subsequent process are also required.

  The lithography cleaning liquid of the present invention has versatility that it can cover a wide range of materials used to form various coating films used in the lithography process and different cleaning applications of multiple cleaning targets, and can be efficiently performed in a short time. As a cleaning solution for lithography, such as cleaning performance that can cleanly remove the object to be cleaned, drying performance that dries quickly in a short time, and no adverse effects on the shape of the remaining film used in the subsequent subsequent processes It has basic characteristics, and also satisfies various required characteristics such as being inexpensive and capable of stable supply, having safety such as low flash point without adversely affecting the environment and the human body.

  Next, the best mode for carrying out the present invention will be described by way of examples, but the present invention is not limited to these.

[Examples 1a to 7a, Comparative Examples 1a to 3a]
TDMR-AR3000 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), i-line resist using novolak resin as a base resin, was applied onto a 300 mm silicon wafer to form a resist film. The base material was subjected to cup cleaning and substrate edge portion (edge) cleaning using the cleaning liquid for lithography shown in Table 1 below. For the cup cleaning, the cleaning process was performed by contacting with the cleaning liquid for 1 minute, and for the edge cleaning, the cleaning process was performed by contacting with the cleaning liquid for 10 seconds. The results are visually observed for cup cleaning, and for edge cleaning, cleaning properties after cleaning, top surface residue, and side surface residue are observed using a CCD camera (manufactured by Keyence Corporation). And evaluated each. The results are shown in Table 1.

[Examples 1b to 7b, Comparative Examples 1b to 3b]
TDUR-P015 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), which is a KrF resist using polyhydroxystyrene as a base resin, was applied on a 300 mm silicon wafer to form a resist film. The base material was subjected to cup cleaning and substrate edge portion (edge) cleaning using the lithography cleaning liquid shown in Table 2 below. For the cup cleaning, the cleaning process was performed by contacting with the cleaning liquid for 1 minute, and for the edge cleaning, the cleaning process was performed by contacting with the cleaning liquid for 10 seconds. The results are visually observed for cup cleaning, and for edge cleaning, cleaning properties after cleaning, top surface residue, and side surface residue are observed using a CCD camera (manufactured by Keyence Corporation). And evaluated each. The results are shown in Table 2.

[Examples 1c to 7c, Comparative Examples 1c to 3c]
On a 300 mm silicon wafer, TARF-P6111 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), which is an ArF resist using an acrylic resin as a base resin, was applied to form a resist film. The base material was subjected to cup cleaning and substrate edge portion (edge) cleaning using the lithography cleaning liquid shown in Table 3 below. For the cup cleaning, the cleaning process was performed by contacting with the cleaning liquid for 1 minute, and for the edge cleaning, the cleaning process was performed by contacting with the cleaning liquid for 10 seconds. The results are visually observed for cup cleaning, and for edge cleaning, cleaning properties after cleaning, top surface residue, and side surface residue are observed using a CCD camera (manufactured by Keyence Corporation). And evaluated each. The results are shown in Table 3.

[Examples 1d to 7d, Comparative Examples 1d to 3d]
TARF-SC127 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), which is a Si-containing resist using a silicon atom-containing polymer as a base resin, was applied onto a 300 mm silicon wafer to form a resist film. The base material was subjected to cup cleaning and substrate edge portion (edge) cleaning using the lithography cleaning liquid shown in Table 4 below. For the cup cleaning, the cleaning process was performed by contacting with the cleaning liquid for 1 minute, and for the edge cleaning, the cleaning process was performed by contacting with the cleaning liquid for 10 seconds. The results are visually observed for cup cleaning, and for edge cleaning, cleaning properties after cleaning, top surface residue, and side surface residue are observed using a CCD camera (manufactured by Keyence Corporation). And evaluated each. The results are shown in Table 4.

[Examples 1e to 7e, Comparative Examples 1e to 3e]
ARC29A (manufactured by Brewer Science), which is an antireflection film forming material using an acrylic polymer as a base resin, was applied on a 300 mm silicon wafer to form an antireflection film. The base material was subjected to cup cleaning and substrate edge portion (edge) cleaning using the lithography cleaning liquid shown in Table 5 below. For the cup cleaning, the cleaning process was performed by contacting with the cleaning liquid for 1 minute, and for the edge cleaning, the cleaning process was performed by contacting with the cleaning liquid for 10 seconds. The results are visually observed for cup cleaning, and for edge cleaning, cleaning properties after cleaning, top surface residue, and side surface residue are observed using a CCD camera (manufactured by Keyence Corporation). And evaluated each. The results are shown in Table 5.

[Examples 1f to 7f, Comparative Examples 1f to 3f]
A protective film was formed by applying TILC-031 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), which is a protective film forming material using a fluorine atom-containing alkali-soluble polymer as a base resin, on a 300 mm silicon wafer. The base material was subjected to cup cleaning and substrate edge portion (edge) cleaning using the lithography cleaning liquid shown in Table 6 below. For the cup cleaning, the cleaning process was performed by contacting with the cleaning liquid for 1 minute, and for the edge cleaning, the cleaning process was performed by contacting with the cleaning liquid for 10 seconds. The results are visually observed for cup cleaning, and for edge cleaning, cleaning properties after cleaning, top surface residue, and side surface residue are observed using a CCD camera (manufactured by Keyence Corporation). And evaluated each. The results are shown in Table 6.

  In Tables 1 to 6, GBL represents γ-butyrolactone, ANS represents anisole, PGME represents propylene glycol monomethyl ether, and PGMEA represents propylene glycol monomethyl ether acetate. Moreover, the unit of the numerical value in the said Tables 1-6 is all the mass%.

In Tables 1 to 6, the evaluation results are as follows.
[Cup cleaning performance]
○: Contaminants attached to the cup could be removed.
X: The contaminant adhering to the inside of the cup could not be removed.
[Edge cleanability]
○: The cleaning performance of the coating film was good.
(Triangle | delta): Although the washing | cleaning removal of the coating film is possible, rattling was seen.
[Edge top surface residue (: Edge residue)]
○: There was no residue.
Δ: There was a residue.
[Edge side residue (: Edge side residue)]
○: There was no residue.
Δ: There was a residue.
●: Drying of the cleaning agent was incomplete, and dry spots were observed.
X: The coating film itself could not be removed.

  From the results of Examples 1a to 5f and Comparative Examples 1a to 3f, by adopting the cleaning liquid composition of the present invention, there is versatility and excellent cleaning performance, and further, there is no adverse effect on the subsequent post process. It turns out that a washing | cleaning liquid is obtained.

[Example 1g, Comparative Example 1g]
ARC29A (made by Brewer Science), which is an antireflection film forming material, is applied onto a 300 mm silicon wafer, and then the substrate edge is cleaned by contacting with a cleaning solution similar to Example 1a and Comparative Example 1a for 10 seconds. Processed. Thereafter, an antireflection film having a thickness of 77 nm was formed by heat treatment at 215 ° C. for 60 seconds. On the antireflection film, a resist composition for ArF, TARF-P6111 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), was applied, and then contacted with the same cleaning solution as in Example 1a and Comparative Example 1a for 10 seconds. The edge was washed. Then, a 215 nm-thick resist film was formed by heat treatment at 130 ° C. for 90 minutes. Further, TILC-031 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), which is a material for forming a protective film, is applied to the upper layer, and then contacted with the same cleaning solution as in Example 1a and Comparative Example 1a for 10 seconds, thereby forming the edge of the substrate. The part was washed. Then, the protective film with a film thickness of 35 nm was formed by heat-processing at 90 degreeC for 60 second. By such treatment, a base material having a stack structure as shown in FIG. 2 was formed.

  With respect to the base material after this treatment, it was observed using a CCD camera (manufactured by Keyence Corporation) from the direction perpendicular to the edge of the substrate. As a result, when the cleaning solution of the present invention was used, good cleaning performance was shown, but when the cleaning solution of the comparative example was used, the shape of the interface of the antireflection film varied and the backlash of the protective film material occurred. Was.

Schematic which shows an example of the stack structure of the coating film in an immersion lithography method. Schematic which shows an example of the stack structure of the coating film in an immersion lithography method.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Silicon wafer 2 Antireflection film 3 Resist film 4 Resist protective film

Claims (10)

  A cleaning liquid for lithography, comprising (A) a glycol organic solvent, (B) a lactone organic solvent, and (C) at least one organic solvent selected from alkoxybenzene and aromatic alcohol.   The lithography cleaning liquid according to claim 1, wherein the component (A) is at least one selected from alkylene glycol alkyl ethers.   The lithography cleaning liquid according to claim 1, wherein the component (A) is propylene glycol monomethyl ether.   The lithographic cleaning liquid according to any one of claims 1 to 3, wherein the component (B) is γ-butyrolactone.   The lithography cleaning liquid according to claim 1, wherein the component (C) is anisole.   The component (A) is 3 to 60% by mass, the component (B) is 3 to 40% by mass, and the component (C) is 20 to 80% by mass. 6. The lithography cleaning liquid according to any one of 5 above.   The lithographic cleaning liquid according to claim 1, wherein the lithographic cleaning liquid is used in a cleaning step in manufacturing a substrate using an immersion lithography method.   A substrate cleaning process comprising: cleaning a substrate using the lithography cleaning liquid according to any one of claims 1 to 7 in a cleaning step in manufacturing a substrate using an immersion lithography method. Method.   Substrate after forming the coating film on the substrate, the step of removing the unnecessary coating film adhering to the substrate rear surface portion or the edge portion or both after forming the coating film on the substrate. 9. The substrate according to claim 8, wherein the substrate is at least one cleaning step selected from a step of removing the entire coating film existing above and a substrate cleaning step before applying the coating film forming material. Cleaning method. In manufacturing a substrate using an immersion lithography method, the chemical liquid supply device for forming a coating film is cleaned using the lithography cleaning liquid according to any one of claims 1 to 7. Cleaning method for a chemical supply apparatus.

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