JP4545553B2 - Non-spin coating positive photoresist composition and resist pattern forming method - Google Patents

Description

  The present invention relates to a positive photoresist composition suitable for a non-spin coating method, and a resist pattern forming method using the same.

Conventionally, in the field of manufacturing liquid crystal display elements using a small glass substrate, a method of spinning after dropping in the center has been used as a resist coating method (the following Non-Patent Document 1).
In the coating method that spins after dropping in the center, the amount of resist used is wasteful, it is difficult to cope with the increase in size of the substrate, and the difference in the resist film thickness between the central portion and the peripheral portion of the substrate tends to increase. Therefore, a new coating method using a discharge nozzle has been proposed as a new resist coating method applicable to a fourth generation substrate (680 mm × 880 mm) or later, particularly a large substrate after the fifth generation substrate.
In this method, a discharge nozzle having a plurality of nozzle holes arranged in a row or a slit-like discharge port and using a discharge nozzle capable of discharging a photoresist composition in a strip shape, the discharge nozzle and the substrate are relative to each other. In this method, the photoresist composition is coated on the entire coated surface of the substrate.

In the coating method using a discharge nozzle, a photoresist composition is deposited on the entire coated surface of the substrate in a larger amount than the coating thickness to be obtained, and then the substrate is spun to adjust to a predetermined coating thickness. In addition to the method, there is a non-spin coating method in which coating is performed while controlling the ejection amount so as to obtain a coating film thickness to be obtained when the ejection nozzle and the substrate are relatively moved.
Electronic Journal August 2002, pages 121-123

As for a coating method using a discharge nozzle, a suitable coating apparatus has recently been developed and announced, and the optimization of a photoresist composition used for such a coating method has become a problem in the future.
In particular, the non-spin coating method is promising as a method that can suitably cope with an increase in the size of the substrate. However, when coating is performed by relatively moving the ejection nozzle and the substrate, the ejection amount is set so that a predetermined coating film thickness is obtained. Therefore, the development of a suitable photoresist composition is important for the practical use of this method.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a positive photoresist composition that can be suitably used in a non-spin coating method, and to provide a method of forming a resist pattern using the same. To do.

When the photoresist composition is applied to the entire coating surface of the substrate by a coating method using a discharge nozzle, the present inventors generate “streak-like marks” on the coating film along the movement direction of the discharge nozzle. It has been found that there is a problem, and in particular, in the non-spin coating method, the occurrence of this streak-like mark tends to be remarkable.
In this regard, in the spin method, the liquid is relatively thick (for example, about 50 to 200 μm) during application, and then the substrate is spun to adjust to an optimum film thickness (for example, about 5 to 40 μm). The film thickness of the coating film is relatively thick, so that the fluidity of the coating film is high, and it is considered that the streak-like marks are not noticeable due to the fluidity of the coating film. On the other hand, in the non-spin coating method, the liquid is deposited thinner than the spin method (for example, about 5 to 40 μm) in order to obtain an optimum film thickness at the time of coating. Therefore, it is considered that the fluidity of the coating film is small and streak marks are likely to occur. Although depending on the solid content concentration of the resist composition, the coating film having a thickness of about 5 to 40 μm becomes a coating film having a thickness of about 0.5 to 8 μm after the drying treatment.
On the other hand, in the non-spin coating method, it has also been found that coating unevenness easily occurs when the fluidity of the coating film is too large.
Furthermore, in the case of the non-spin coating method, it is necessary to discharge a very small amount of coating liquid (photoresist composition) from the discharge nozzle while strictly controlling the discharge amount. It has also been found that it is difficult to always discharge the liquid in a uniform amount, and there is a problem that liquid breakage is likely to occur during the discharge.
As a result of extensive research, the present inventors have made the viscosity of the resist composition within a specific range, so that in the non-spin coating method, the generation of streak marks, the occurrence of coating unevenness, and the discharge It has been found that prevention of liquid breakage can be achieved, and the present invention has been achieved.

（Ｒ ^１ は炭素原子数１〜３のアルキル基、Ｒ ^２ は炭素原子数１〜１５のアルキル基を表す）
で表される繰返し単位と、下記一般式（２）

（Ｒ ^１ は炭素原子数１〜３のアルキル基、Ｒ ^３ はポリエステル変性基を表す）
で表される繰返し単位とを含有するポリエステル変性ポリジアルキルシロキサン系界面活性剤とを含有してなり、当該組成物の粘度が１〜１０ｃｐであることを特徴とする。 That is, in order to achieve the above object, the positive photoresist composition for non-spin coating method of the present invention has a positive photoresist composition on the entire coated surface of the substrate by relatively moving the discharge nozzle and the substrate. a positive photoresist composition for use in Nonsupin coating method having a step of applying, (a) an alkali-soluble resin, and (B) a naphthoquinone diazide esterified product, and (D) an organic solvent, (E1) represented by the following general formula (1)

(R ¹ represents an alkyl group having 1 to 3 carbon atoms, and R ² represents an alkyl group having 1 to 15 carbon atoms)
A repeating unit represented by the following general formula (2)

(R ¹ represents an alkyl group having 1 to 3 carbon atoms, and R ³ represents a polyester-modified group)
And a polyester-modified polydialkylsiloxane surfactant containing a repeating unit represented by the formula: wherein the composition has a viscosity of 1 to 10 cp.

In addition, the present invention includes a step of applying the positive photoresist composition for non-spin coating method of the present invention with a predetermined coating thickness to the entire coating surface of the substrate by relatively moving the discharge nozzle and the substrate. A method for forming a resist pattern is provided.

According to the positive photoresist composition of the present invention, when a photoresist composition is applied on a substrate so as to have a predetermined coating thickness by a non-spin coating method using a discharge nozzle, streaks or coatings are applied to the coating film. Unevenness can be suppressed. In addition, it is possible to prevent the liquid from being discharged from the discharge nozzle, and a resist film having excellent film thickness uniformity can be obtained.
Therefore, the positive photoresist composition of the present invention can be suitably used for the non-spin coating method.
According to the resist pattern forming method of the present invention, the positive photoresist composition can be applied to the entire coating surface of the substrate by a non-spin coating method using a discharge nozzle so as to have a predetermined coating thickness. A resist film having excellent thickness uniformity can be formed. In addition, since a step of spinning the substrate after application is not required, it can be applied to a large substrate.

The present invention will be described in detail below.
The “non-spin coating method” in the present specification is a method having a step of coating a positive photoresist composition with a predetermined coating film thickness on the entire coating surface of the substrate by relatively moving the discharge nozzle and the substrate. Specifically, there are a method using a nozzle having a plurality of nozzle holes arranged in a row, a method using a nozzle having a slit-like discharge port, and the like.
In the non-spin coating method, a coating film having a predetermined thickness (coating film thickness) is formed on a substrate by a coating method using a discharge nozzle. This coating film is dried to obtain a resist film. The coating film thickness (predetermined thickness) is set to be larger than the thickness of the resist film to be obtained in consideration of the film thickness reduction during drying.

In the present specification, the “substrate coating surface” refers to a region of the substrate to which the resist composition is to be coated, and is generally the entire surface of the substrate.
The “structural unit” in the present specification indicates a monomer unit constituting a polymer (resin).
The value of the viscosity in this specification is a value measured under a condition of 25 ° C. using a Canon Fenske viscometer.

Component (A) The alkali-soluble resin (A) used in the present invention is not particularly limited, and can be arbitrarily selected from those that can be normally used as a film-forming substance in a positive photoresist composition. Preferable examples include novolak resins, polyhydroxystyrene and derivatives thereof obtained by condensation reaction of aromatic hydroxy compounds and aldehydes or ketones.
As the alkali-soluble resin (A), an alkali-soluble novolak resin is preferably used, and in particular, an alkali-soluble novolak resin prepared so that a polystyrene-equivalent mass average molecular weight (hereinafter referred to as only Mw) is 6000 or more is used. It is preferable in terms of more effectively preventing the occurrence of streak-like marks in the non-spin coating method. The more preferable range of Mw of the alkali-soluble novolak resin used as the component (A) is about 6000 to 10,000.

Specific examples of the alkali-soluble novolak resin include novolak resins obtained by reacting phenols exemplified below with aldehydes exemplified below in the presence of an acid catalyst.
Examples of the phenols include phenol; cresols such as m-cresol, p-cresol, and o-cresol; 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, and the like. Xylenols; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2- alkylphenols such as tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxy Alkoxyphenols such as enol and m-propoxyphenol; isopropenylphenols such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol and 2-ethyl-4-isopropenylphenol; Examples include arylphenols such as phenylphenol; polyhydroxyphenols such as 4,4′-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, and pyrogallol. These may be used alone or in combination of two or more. Among these phenols, m-cresol and p-cresol are particularly preferable.

Examples of the aldehydes include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanealdehyde, furfural, furylacrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropyl. Aldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p- Chlorobenzaldehyde, cinnamon Examples include aldehyde. These may be used alone or in combination of two or more. Among these aldehydes, formaldehyde is preferable because of its availability.
As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, oxalic acid, p-toluenesulfonic acid and the like can be used.

  When the component (A) is composed of a novolak resin, one kind of novolak resin may be used, or two or more kinds of novolak resins may be mixed. When two or more kinds of novolak resins are used, the Mw of each novolak resin is not particularly limited, but it is preferably prepared so that the Mw is within the range of 6000 or more as the whole component (A).

(A1), (A2)
When component (A) is composed of a novolak resin, formaldehyde is used as a condensing agent for (A) mixed phenols of m-cresol / p-cresol = 20/80 to 40/60 (preparation ratio). Synthesized novolak resin (A1) having Mw of 4000 to 6000 and mixed phenols of m-cresol / p-cresol = 20/80 to 40/60 (preparation ratio) were synthesized using formaldehyde as a condensing agent. The Mw is 5,000 to 10,000, and the high-sensitivity resist composition contains at least one novolak resin selected from the novolak resins (A2) having a higher molecular weight than (A1). It is preferable from the viewpoint of being suitable for preparation and improving the remaining film property of the unexposed area. In (A1) and (A2), the ratio of m-cresol / p-cresol (preparation ratio) is particularly preferably 25/75 to 35/65. Part of p-cresol used in the reaction is present in the reaction system as an unreacted substance or a binuclear substance, and is removed during the fractionation operation for the purpose of cutting a low molecular weight substance after completion of the synthesis reaction. A preferable monomer ratio of m-cresol structural unit / p-cresol structural unit in the finally obtained novolak resin is about 25/75 to 45/55, particularly about 30/70 to 40/60.

The Mw of the components (A1) and (A2) is such that the Mw is 4000 to 6000, particularly 4500 to 5500 in terms of increasing the sensitivity of the resist composition and improving the remaining film ratio. The latter (A2) is preferably 5000 to 10000, particularly 5500 to 6500.
In the case of using at least one component (novolak resin) selected from the components (A1) and (A2), the preferred total content ratio of the components (A1) and (A2) in the component (A) is 10 to 10. It is 60 mass%, More preferably, it is 45-55 mass%. When the total content ratio of the component (A1) and the component (A2) in the component (A) is outside the above range, it is difficult to obtain the effect of increasing the sensitivity and the remaining film ratio.

(A3)
Moreover, when (A) component consists of novolak resin, formaldehyde is used as a condensing agent for mixed phenols of m-cresol / p-cresol = 50/50 to 70/30 (preparation ratio) in component (A). It is preferable from the point which is excellent in the effect which suppresses generation | occurrence | production of a stripe-shaped mark that Mw synthesize | combined using and containing 9000 or more novolak resin (A3) is contained. The m-cresol / p-cresol ratio (preparation ratio) is particularly preferably 55/45 to 65/35. Part of p-cresol used in the reaction is present in the reaction system as an unreacted substance or a binuclear substance, and is removed during the fractionation operation for the purpose of cutting a low molecular weight substance after completion of the synthesis reaction. The preferable monomer ratio of m-cresol structural unit / p-cresol structural unit in the finally obtained novolak resin is about 55/45 to 75/25, particularly about 60/40 to 70/30.
If the Mw of the component (A3) is too large, the sensitivity of the resist composition may be adversely affected and the resist pattern releasability in the resist pattern peeling process may be adversely affected. Is small, Mw is preferably 9000 or more, more preferably 9500 to 15000.
When (A3) component is used, the preferable content rate of (A3) component in (A) component is 40-90 mass%, More preferably, it is 45-55 mass%. When the content ratio of (A3) in the component (A) is larger than the above range, the sensitivity of the resist composition may be lowered and the resist pattern may be adversely affected in the resist pattern peeling process. The effect of suppressing the generation of scars is poor.

  In this invention, it is preferable that (A) component contains three types of the said (A1) component, (A2) component, and (A3) component. In this case, the content ratio of the component (A1), the component (A2) and the component (A3) is within the range of [(A1) + (A2)] / (A3) = 10/90 to 60/40 in terms of mass ratio. Preferably, the range of 45/55 to 55/45 is more preferable.

  Moreover, you may make the (A) component contain novolak resin other than (A1), (A2), and (A3) if desired. The preferable content ratio of the total of (A1), (A2), and (A3) in the component (A) is 50% by mass or more, and more preferably 90% by mass or more. It may be 100% by mass.

(B) Component (B) The naphthoquinone diazide group-containing compound in the present invention is a photosensitive component. As this (B) component, what was conventionally used as a photosensitive component of the positive photoresist composition for liquid crystal display element manufacture can be used, for example.
For example, as the component (B), an esterification reaction product of a phenolic hydroxyl group-containing compound represented by the following formula (I) and a 1,2-naphthoquinonediazide sulfonic acid compound is very inexpensive and highly sensitive. It is preferable in that the photoresist composition can be prepared.
The average esterification rate of this esterification reaction product is 50 to 70%, preferably 55 to 65%. If it is less than 50%, film loss after development tends to occur, and there is a problem in that the remaining film rate is lowered. If it exceeds 70%, the storage stability tends to decrease, which is not preferable.
The 1,2-naphthoquinonediazide sulfonic acid compound is preferably a 1,2-naphthoquinonediazide-5-sulfonyl compound.

In addition to the above photosensitive component, other quinonediazide esterified products can be used as the component (B), but the amount used thereof is 30% by mass or less, particularly 25% by mass or less in the component (B). Preferably there is.
As other quinonediazide esterified products, for example, a phenolic hydroxyl group-containing compound represented by the following general formula (II) and a 1,2-naphthoquinonediazidesulfonic acid compound, preferably a 1,2-naphthoquinonediazide-5-sulfonyl compound or 1 An esterification reaction product with 2-naphthoquinonediazide-4-sulfonyl compound can be used.
These may use any 1 type and may use 2 or more types together.

[Wherein R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. R ^{9 to} R ¹¹ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Q is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or R ⁹ to be bonded to a carbon atom. A cycloalkyl group having a chain of 3 to 6, or a residue represented by the following chemical formula (III)

Wherein R ¹² and R ¹³ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. C represents an integer of 1 to 3); a and b represent an integer of 1 to 3; d represents an integer of 0 to 3; and n represents an integer of 0 to 3]

  The compounding amount of the component (B) in the photoresist composition of the present invention is 15 to 40 parts by mass, preferably 100 parts by mass of the total amount of the alkali-soluble resin (A) and the phenolic hydroxyl group-containing compound (C) described later, preferably It is preferable to be within the range of 20 to 30 parts by mass. When the content of the component (B) is less than the above range, the transferability is greatly lowered, and a resist pattern having a desired shape is not formed. On the other hand, when the amount is larger than the above range, sensitivity and resolution are deteriorated, and a residue is easily generated after development processing.

Component (C) The positive photoresist composition of the present invention preferably contains a phenolic hydroxyl group-containing compound (C) having a molecular weight of 1000 or less. Thereby, the sensitivity improvement effect is acquired. In particular, in the field of liquid crystal display device manufacturing, improvement of throughput is a very big problem, and resist consumption tends to increase, so that a photoresist composition is highly sensitive and inexpensive. Desirably, it is preferable to use the component (C) because high sensitivity can be achieved at a relatively low cost. In addition, when the component (C) is contained, a surface hardly-solubilized layer is strongly formed in the resist pattern, so that the amount of unremoved resist film in the unexposed portion is small during development, and development unevenness occurs due to the difference in development time. It is suppressed and preferable.

When the molecular weight of the component (C) exceeds 1000, the sensitivity tends to decrease greatly, such being undesirable.
As the component (C), a phenolic hydroxyl group-containing compound having a molecular weight of 1000 or less, which is conventionally used in positive photoresist compositions for producing liquid crystal display elements, can be used as appropriate, and is represented by the above general formula (II). The phenolic hydroxyl group-containing compound is more preferable because it can effectively improve sensitivity. (C) A component may be 1 type and may use 2 or more types together.

  Among the phenolic hydroxyl group-containing compounds represented by the general formula (II), a compound represented by the following formula (IV) is particularly preferable because it is excellent in increasing sensitivity and increasing the remaining film ratio.

  (C) The compounding quantity of a component is 1-25 mass parts with respect to 100 mass parts of (A) component, Preferably the range of 5-20 mass parts is preferable. If the content of the component (C) in the photoresist composition is too small, the effect of improving the sensitivity and the remaining film ratio cannot be sufficiently obtained, and if it is too much, a residue is likely to be generated on the substrate surface after development. Also, the raw material cost is increased, which is not preferable.

(D) Component The composition of the present invention is used in the form of a solution by dissolving the components (A) to (C) and various additive components in the organic solvent (D).
As the organic solvent (D) used in the present invention, propylene glycol monomethyl ether acetate (PGMEA), particularly one containing PGMEA and an organic solvent having a higher boiling point than the PGMEA is preferably used. By using such a high-boiling organic solvent in combination, it is possible to prevent the phenomenon of solvent drying unevenness (coating unevenness) on the film surface and the occurrence of streak-like marks.
The high-boiling organic solvent is not particularly limited as long as it has a boiling point higher than that of PGMEA and has a low evaporation rate, but among them ethyl pyruvate (PE), ethyl lactate (NE), and 3-methoxybutyl. At least one selected from acetate (MBA) is desirable because it is highly effective in reducing the solvent drying unevenness (coating unevenness) on the film surface and preventing the phenomenon of streaking, and MBA is most preferable.
In component (D), the proportion of the total of PGMEA and the high-boiling organic solvent is preferably 90% by mass or more, and if it is less than this, the effect of reducing unevenness of solvent drying (coating unevenness) on the film surface and streak-like marks Suppressive effect is poor.
The mass ratio between PGMEA and the high boiling organic solvent (PGMEA / high boiling organic solvent) is preferably in the range of 10/1 to 1/1, and more preferably in the range of 10/1 to 2/1.

The component (D) may contain other organic solvents other than PGMEA and the high boiling organic solvent, but the component (D) is a mixed solvent composed of one or more of PGMEA and the high boiling organic solvent. More preferably.
As the organic solvent other than PGMEA and the above high-boiling organic solvent, those conventionally used as organic solvents for positive photoresist compositions for producing liquid crystal display elements can be appropriately used. Examples thereof include γ-butyrolactone and propylene glycol monobutyl ether.

(E) component In this invention, surfactant (E) can be contained in a photoresist composition. In order to effectively prevent the generation of streak-like marks in the non-spin coating method, (1) the surfactant content is 900 ppm or less, preferably 0, based on the entire photoresist composition. It is desirable to select either of (1) the surfactant (E1) or (3) the specific surfactant (E2).
In the case of (1) above, the surfactant content is preferably in the range of 100 to 800 ppm, more preferably in the range of 200 to 700 ppm.
By setting the content of the surfactant (E) to 900 ppm or less, the generation of streak-like marks in the non-spin coating method can be effectively prevented. In terms of suppressing streaks, it is preferable that the amount of the surfactant is small, and 0 is desirable.

  There is no restriction | limiting in particular as surfactant (E) in the case of said (1), For example, the compound conventionally known as surfactant for resist can be used 1 type (s) or 2 or more types. As the surfactant, fluorine-silicon based surface activity is suitable. For example, a nonionic fluorine-silicon surfactant in which a perfluoroalkyl ester group, an alkylsiloxane group, an ethyleneoxy group, and a propyleneoxy group are bonded can be used. Examples of the surfactant include Megafac R-08 and R-60 (product name, manufactured by Dainippon Ink & Chemicals, Inc.).

Component (E1) In the case of (2) above, the specific surfactant contains a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2). Examples include polyester-modified polydialkylsiloxane surfactants. When the (E1) is contained in the photoresist composition, the generation of streak-like marks in the non-spin coating method can be effectively prevented. It is also effective for film thickness uniformity.
In addition, when the component (E1) is contained, when a photoresist composition is applied on a highly reflective metal film, such as when a metal film to be a gate electrode is formed on a transparent glass substrate, the substrate is applied after application. When the resist film formed on the top is observed from above, it is possible to effectively suppress the inconvenience that a dull pattern (moy) occurs.

(R ¹ represents a linear or branched alkyl group having 1 to 3 carbon atoms, and R ² represents a linear or branched alkyl group having 1 to 15 carbon atoms)

(R ¹ represents a linear or branched alkyl group having 1 to 3 carbon atoms, and R ³ represents a polyester-modified group)

The component (E1) is not particularly limited as long as it is a siloxane surfactant containing a repeating unit represented by the above general formula, and may contain a unit other than the repeating unit. However, in order to achieve the object of the present invention, the repeating unit represented by the above general formula is preferably the main component, and the silicon atom at the end of the polymer is represented by the following general formula (3) It is preferable that
Among the repeating units constituting the component (E1), the content of the repeating unit represented by the above general formula is preferably 10 mol% or more, and may be 100 mol%.

(In the formula, R ¹ is a linear or branched alkyl group having 1 to 3 carbon atoms.)

  Specific examples of (E1) include trade names BYK-310 and BYK-315 (both manufactured by Big Chemie). Among these, BYK-310 is particularly preferable because it can effectively suppress generation of haze and stripes (streak-like marks).

The blending amount of the component (E1) is a solid content excluding the organic solvent (D) and the component (E) in the photoresist composition in order to effectively and efficiently achieve uniform film thickness of the resist film. Is preferably 0.001 to 1% by mass, and is particularly preferably 0.02 to 0.5% by mass for the purpose of suppressing the occurrence of streak-like marks, and particularly for the purpose of suppressing the occurrence of haze unevenness. Is preferably in the range of 0.2 to 0.5 mass%.
When using (E1), it is preferable to occupy 25% by mass or more in the component (E). It may be 100% by mass.

(E2) Component The specific surfactant in the case of (3) above includes surfactants having a fluorine content of 10 to 25% by mass and a silicon content of 3 to 10% by mass. When (E2) is contained, the generation of streak-like marks in the non-spin coating method can be effectively prevented.
The fluorine content in the component (E2) is a numerical value obtained by ion chromatography after forming fluorine ions. The silicon content is a numerical value obtained by inductively coupled plasma optical emission spectrometry (ICP).
More specifically, the fluorine content is quantified by ion chromatography after the sample is heated in an electric furnace to burn carbon and hydrogen to generate fluorine ions. Further, the silicon content is quantified by preparing a sample as a solid or a solution and using the ICP method.

  A more preferable range of the fluorine content in the component (E2) is 15 to 25% by mass. A more preferable range of the silicon content is 5 to 10% by mass. (E2) Those having a fluorine content of 2 to 5 times the silicon content in the component are more preferred.

The component (E2) is not particularly limited as long as it satisfies the fluorine content and silicon content in the above ranges, but preferred specific examples include trade names X-70-090, X-70-091, Nonionic fluorine / silicone surfactants in which a perfluoroalkyl group, an alkylsiloxane group, and an alkyleneoxy group, such as X-70-092 and X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.), are bonded. Can be mentioned. The specific examples given here all have a fluorine content of 21% by mass and a silicon content of 7% by mass.
Among these, in particular, X-70-093 is more preferable because it has a high effect of suppressing the occurrence of uneven film thickness due to streak-like marks and drying unevenness even when the amount of the photoresist composition applied is small.

The blending amount of the component (E2) excludes the organic solvent (D) and the component (E) in the photoresist composition in order to effectively and efficiently prevent the generation of streak marks in the non-spin coating method. It is preferable to set it as the range of 0.001-1 mass% with respect to solid content, Preferably it is 0.02-0.5 mass%.
When using (E2), it is preferable to occupy 25% by mass or more in the component (E). It may be 100% by mass.

Other Components Various additives such as a storage stabilizer can be used in the composition of the present invention as long as the object of the present invention is not impaired.
For example, UV absorbers for preventing halation, such as 2,2 ′, 4,4′-tetrahydroxybenzophenone, 4-dimethylamino-2 ′, 4′-dihydroxybenzophenone, 5-amino-3-methyl-1-phenyl -4- (4-hydroxyphenylazo) pyrazole, 4-dimethylamino-4′-hydroxyazobenzene, 4-diethylamino-4′-ethoxyazobenzene, 4-diethylaminoazobenzene, curcumin and the like can be appropriately contained.

Moreover, the adhesive improvement agent for improving the adhesiveness of the layer which consists of a photoresist composition, and its lower layer can be contained suitably. As the adhesion improver, 2- (2-hydroxyethyl) pyridine is preferable, and when a resist pattern is formed on a metal film such as a Cr film by appropriately containing this in a photoresist composition, a photoresist composition is used. It is possible to effectively improve the adhesion between the material layer and the metal film.
When the adhesion improver is contained, if the amount is too large, the change over time of the resist composition tends to deteriorate, and if it is too small, the effect of improving the adhesion cannot be sufficiently obtained. It is preferable to be within the range of 0.1 to 10% by mass.

The photoresist composition of the present invention is prepared such that its viscosity is 1 to 10 cp (10 to 100 Pa · s), preferably 2 to 6 cp (20 to 60 Pa · s). When the viscosity of the photoresist composition exceeds 10 cp, streaks and liquid breakage during ejection are likely to occur when the photoresist composition is applied onto the substrate by a non-spin coating method using a discharge nozzle. On the other hand, if the viscosity is less than 1 cp, uneven coating tends to occur remarkably, and the film thickness uniformity may be deteriorated. A more preferable range of the viscosity of the photoresist composition is 2.5 to 5 cp.
Further, the solid content concentration of the photoresist composition of the present invention is preferably 7 to 20% by mass, and more preferably 8 to 18% by mass. When the solid content concentration exceeds the above range, when a photoresist composition is applied onto a substrate by a non-spin coating method using a discharge nozzle, streak marks and liquid breakage during discharge are likely to occur. On the other hand, if the solid content concentration is lower than the above range, uneven coating tends to occur, and the film thickness uniformity tends to deteriorate.
The viscosity and solid content concentration of the photoresist composition can be adjusted by appropriately controlling, for example, the molecular weight of the resin component, the solid content molecular weight of the resist composition, the type of organic solvent (D), and the amount of use thereof. it can.

The photoresist composition having such a configuration is suitable for a non-spin coating method using a discharge nozzle, and when the photoresist composition is discharged in a strip shape from the discharge nozzle and applied onto a substrate, streaks and uneven coating are suppressed. And good film thickness uniformity in the coating film can be achieved. Moreover, it is possible to prevent the liquid from running out during discharge.
According to the photoresist composition of the present invention, even when the coating film thickness (before the drying treatment) is controlled to, for example, about 5 to 40 μm, preferably about 10 to 30 μm, no liquid breakage occurs, It is possible to prevent streaks and uneven coating.

Hereinafter, an embodiment of a resist pattern forming method of the present invention will be described.
The method for forming a resist pattern of the present invention comprises a step of applying the positive photoresist composition of the present invention on a substrate using a non-spin coating method. This coating process can be performed by an apparatus provided with a means for relatively moving the discharge nozzle and the substrate. The discharge nozzle is not particularly limited as long as the photoresist composition discharged from the discharge composition is applied on the substrate in a band shape. For example, a plurality of nozzle holes are arranged in a line. A discharge nozzle having a discharge port or a discharge nozzle having a slit-shaped discharge port can be used. A coating and non-spin type TR63000S (product name; manufactured by Tokyo Ohka Kogyo Co., Ltd.) is known as a coating apparatus having the coating process.

A well-known method can be appropriately used as a step for forming a resist pattern after applying the positive photoresist composition to the entire coated surface of the substrate in this way. For example, a substrate coated with the photoresist composition is heated and dried (prebaked) at about 100 to 140 ° C. to form a resist film. Thereafter, the resist film is selectively exposed through a desired mask pattern. As the wavelength during exposure, ghi line (g line, h line, and i line) or i line can be suitably used, and an appropriate light source is used for each.
Thereafter, the resist coating after selective exposure is developed using a developer composed of an alkaline aqueous solution, for example, a 1 to 10% by mass tetramethylammonium hydroxide (TMAH) aqueous solution.
As a method of bringing the developer solution into contact with the resist film, for example, a method in which liquid is accumulated from one end of the substrate to the other end, or a developing droplet lower nozzle installed near the center of the substrate is applied to the entire surface of the substrate. A method of spreading the developer can be used.
And after leaving still for about 50 to 60 seconds and developing, a resist pattern is obtained by performing the rinse process which rinses off the developing solution which remained on the resist pattern surface using rinse solutions, such as a pure water.

According to such a resist pattern forming method, since a non-spin coating method is used, a resist film can be formed on the substrate without deteriorating coating uniformity and tact time even when the substrate size and device size are increased. Can be formed.
In addition, the photoresist composition used is suitable for the non-spin coating method, and it is possible to prevent the occurrence of streak marks and coating unevenness in the photoresist film and to obtain good film thickness uniformity. In addition, it is possible to prevent liquid from running out during discharge.

Various characteristics of the positive photoresist composition were determined as follows.
(1) Evaluation of streaks:
A sample (positive photoresist composition) was applied on a glass substrate (1100 × 1250 mm ² ) on which a Cr film was formed using a non-spin coating system coating apparatus (product name: TR63000S, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Thus, a coating film was formed.
Next, the temperature of the hot plate is set to 130 ° C., the first drying is performed for 60 seconds by proximity baking with an interval of about 1 mm, and then the temperature of the hot plate is set to 120 ° C. with an interval of 0.5 mm. A second drying for 60 seconds was performed by proximity baking to form a resist film having a thickness of 1.5 μm.
The surface of the obtained resist film was observed under a sodium light source, and the case where no streak formation was observed was shown as ◯, the case where it was slightly generated was shown as Δ, and the case where it was generated was shown as x.

(2) Evaluation of film thickness uniformity:
A sample (positive photoresist composition) was coated on a glass substrate (1100 × 1250 mm ² ) on which a Cr film was formed using a coating apparatus (product name: TR63000S, manufactured by Tokyo Ohka Kogyo Co., Ltd.).
Next, the temperature of the hot plate is set to 130 ° C., the first drying is performed for 60 seconds by proximity baking with an interval of about 1 mm, and then the temperature of the hot plate is set to 120 ° C. with an interval of 0.5 mm. A second drying for 60 seconds was performed by proximity baking to form a resist film having a thickness of 1.5 μm.
Next, the obtained coating film was evaluated for film thickness uniformity by an optical film thickness measurement method using a film thickness measurement device (manufactured by Nanometrics; product name “Nanospec”).

(3) Evaluation of solvent drying unevenness (coating unevenness):
A sample (positive photoresist composition) was coated on a glass substrate (1100 × 1250 mm ² ) on which a Cr film was formed using a coating apparatus (product name: TR63000S, manufactured by Tokyo Ohka Kogyo Co., Ltd.).
Next, the temperature of the hot plate is set to 130 ° C., the first drying is performed for 60 seconds by proximity baking with an interval of about 1 mm, and then the temperature of the hot plate is set to 120 ° C. with an interval of 0.5 mm. A second drying for 60 seconds was performed by proximity baking to form a resist film having a thickness of 1.5 μm.
The surface of the obtained resist film was observed under a sodium light source. The results were shown in the table as “O” when the occurrence of solvent drying unevenness was not observed, “Δ” when slightly generated, and “X” when many were generated.

(Examples 1-9, Comparative Example 1)
As examples and comparative examples, photoresist compositions were prepared with the formulations shown in Table 1 below, and streak-like marks and film thickness uniformity were evaluated. In addition, since the film thickness becomes non-uniform | heterogenous when application | coating nonuniformity and liquid cutting | disconnection generate | occur | produce, it can evaluate about application | coating nonuniformity and liquid cutting | disconnection by evaluation of film thickness uniformity. The evaluation results are shown in Table 2 below.

As the component (A), the following (a1) to (a3) were used. (A) Let the compounding quantity of a component be 100 mass parts. In Table 1, (//) indicates a mixture mixed at the mass ratio described therein.
(A1): A novolak resin obtained by subjecting a mixed phenol of m-cresol / p-cresol = 30/70 to a condensation reaction by a conventional method using formaldehyde as a condensing agent and an oxalic acid catalyst is water-methanol. A novolak resin having an Mw of 5000 obtained by fractionation with a mixed solvent.
(A2): A novolak resin obtained by subjecting a mixed phenol of m-cresol / p-cresol = 30/70 to a condensation reaction by a conventional method using formaldehyde as a condensing agent and an oxalic acid catalyst is water-methanol. Mw 6300 novolac resin obtained by fractionation with a mixed solvent.
(A3): A novolak resin obtained by subjecting a mixed phenol of m-cresol / p-cresol = 60/40 to a condensation reaction by a conventional method using formaldehyde as a condensing agent and an oxalic acid catalyst is water-methanol. A novolak resin having an Mw of 11000 obtained by fractionation with a mixed solvent.

As component (B), 29.7 parts by mass of the following (b1) and / or (b2) were used.
(B1): An esterification reaction product of 1 mol of the phenolic hydroxyl group-containing compound represented by the above formula (I) and 2.34 mol of 1,2-naphthoquinonediazide-5-sulfonyl chloride.
(B2): Esterification reaction of 1 mol of bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) -3,4-dihydroxyphenylmethane and 2.11 mol of 1,2-naphthoquinonediazide-5-sulfonyl chloride Product.

As the component (C), 10 parts by mass of the following (c1) was used.
(C1): Phenolic hydroxyl group-containing compound represented by the above formula (IV) (molecular weight (M) = 376)

As the component (D) (organic solvent), the following (d1) to (d3) were used so as to have the viscosity and solid content concentration shown in Table 1. In Table 1, (//) indicates a mixed solvent mixed at a mass ratio described therein.
(D1): Propylene glycol monomethyl ether acetate (PGMEA)
(D2): 3-methoxybutyl acetate (MBA)
(D3): Ethyl lactate (NE)

600 ppm of the following (e1) was used as the component (E) (surfactant).
(E1): BYK-310 (manufactured by Big Chemie)
As another component, 0.25 mass part of 2- (2-hydroxyethyl) pyridine was used with respect to the total solid content.

  After the above components (A) to (D) and other components are uniformly dissolved, a surfactant (E) is added, and this is filtered using a membrane filter having a pore size of 0.2 μm to form a positive photoresist composition. A product was prepared.

Claims (6)

A positive photoresist composition used in a non-spin coating method having a step of applying a positive photoresist composition to the entire coated surface of a substrate by relatively moving a discharge nozzle and the substrate,
And (A) an alkali-soluble resin,
(B) a naphthoquinone diazide ester,
( D) an organic solvent ;
(E1) The following general formula (1)

(R ¹ represents an alkyl group having 1 to 3 carbon atoms, and R ² represents an alkyl group having 1 to 15 carbon atoms)
A repeating unit represented by the following general formula (2)

(R ¹ represents an alkyl group having 1 to 3 carbon atoms, and R ³ represents a polyester-modified group)
A polyester-modified polydialkylsiloxane surfactant containing a repeating unit represented by :
A positive photoresist composition for a non-spin coating method, wherein the composition has a viscosity of 1 to 10 cp.   2. The positive photoresist composition for non-spin coating method according to claim 1, wherein the viscosity of the composition is 2 to 6 cp.   3. The positive photoresist composition for non-spin coating method according to claim 1, wherein the solid content concentration of the composition is 7 to 20% by mass.   4. The positive photoresist composition for non-spin coating method according to any one of claims 1 to 3, wherein the organic solvent (D) contains propylene glycol monomethyl ether acetate. The positive photoresist for a non-spin coating system according to any one of claims 1 to 4 , wherein the component (A) is an alkali-soluble novolak resin having a polystyrene-equivalent mass average molecular weight (Mw) of 6000 or more. Composition. The positive-type photoresist composition for non-spin coating method according to any one of claims 1 to 5 is applied with a predetermined coating film thickness over the entire coating surface of the substrate by relatively moving the discharge nozzle and the substrate. A method for forming a resist pattern comprising the step of: