JP4209297B2 - POSITIVE PHOTORESIST COMPOSITION FOR DISCHARGE NOZZLE TYPE COATING METHOD AND METHOD FOR FORMING RESIST PATTERN - Google Patents

Description

  The present invention relates to a positive photoresist composition suitable for a discharge nozzle type coating method and a method for forming a resist pattern.

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).
With the coating method that spins after dropping at the center, good coating uniformity can be obtained, but in the case of a large substrate of 1 m square class, for example, the amount of resist that is shaken off during spinning (during spinning) and discarded is considerably increased. In addition, there are problems of cracking of the substrate due to high speed rotation and securing of tact time. Furthermore, since the coating performance in the method of spinning after the central dropping depends on the rotational speed at the time of spinning and the coating amount of the resist, it is intended to be applied to a fifth generation substrate (about 1000 mm × 1200 mm to 1280 mm × 1400 mm) that is further enlarged. Then, there is no general-purpose motor capable of obtaining the necessary acceleration, and there is a problem that the cost of parts increases when such a motor is specially ordered.
In addition, even if the substrate size and the apparatus size are increased, the required performance in the coating process, such as coating uniformity ± 3%, tact time 60 to 70 seconds / sheet, etc., is not substantially changed. It has become difficult to meet demands other than coating uniformity.

Under such circumstances, a resist coating method using a discharge nozzle method 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.
The discharge nozzle type resist coating method is a method in which a positive photoresist composition is applied to the entire coated surface of a substrate by relatively moving the discharge nozzle and the substrate. For example, a plurality of nozzle holes are arranged in a line. There has been proposed a method using a discharge nozzle that has a discharge port and a slit-like discharge port, and can discharge a photoresist composition in a strip shape. In addition, a method has been proposed in which a photoresist composition is applied to the entire coated surface of a substrate by a discharge nozzle method, and then the thickness of the substrate is adjusted by spinning the substrate.
Electronic Journal August 2002, pages 121-123

  With regard to the discharge nozzle type coating method, a suitable coating apparatus has recently been developed and announced, and the optimization of the photoresist composition used in such a coating method has become an important issue in the future.

  The present invention has been made in view of the above circumstances, and provides a positive photoresist composition that can be suitably used in a discharge nozzle type coating method and a method for forming a resist pattern using the same. Objective.

The present inventors have newly found that when a photoresist composition is applied to the entire coated surface of the substrate by a discharge nozzle type coating method, streaky marks may be formed on the coated film. It has also been found that streak-like marks are easily formed in the central portion of the substrate, particularly when the substrate is spun. And it has also been found that the generation of the streak-like traces can be suppressed by forming a thick coating film before spinning, but this increases the amount of resist coating, and thus particularly suppresses resist consumption (resisting energy savings). However, it is difficult to apply in the field of manufacturing liquid crystal display elements in recent years.
Accordingly, as a result of further earnest research, a photoresist composition is prepared using an organic solvent containing propylene glycol monomethyl ether acetate (PGMEA), particularly an organic solvent containing propylene glycol monomethyl ether acetate and an organic solvent having a boiling point higher than that of PGMEA. Thus, when the photoresist composition is ejected from the ejection nozzle and applied onto the substrate, it has been found that the generation of streak-like marks can be prevented while preferably suppressing the resist coating amount, and the present invention has been achieved.

That is, the positive photoresist composition for the discharge nozzle type coating method of the present invention has a step of applying the positive photoresist composition over the entire coating surface of the substrate by relatively moving the discharge nozzle and the substrate. It is used in a coating method and is applied to a glass substrate having a size of 1000 × 1200 mm square or more, (A) an alkali-soluble novolac resin, (B) a phenolic hydroxyl group-containing compound having a molecular weight of 1000 or less, (C) a naphthoquinonediazide group-containing compound and (D) an organic solvent, wherein the (D) organic solvent contains propylene glycol monomethyl ether acetate and an organic solvent having a boiling point higher than that of the propylene glycol monomethyl ether acetate And the high boiling point organic solvent is ethyl lactate and 3-methoxybutyrate. At least one selected from the group consisting of Le acetate, and the (D) the total amount of occupied organic solvent propylene glycol monomethyl ether acetate and an organic solvent of the high boiling point, Ru der least 90 mass% This is a positive photoresist composition for a discharge nozzle type coating method.

  Further, the present invention uses a discharge nozzle type coating method in which a positive photoresist composition is applied to the entire coating surface of a substrate by relatively moving the discharge nozzle and the substrate. There is provided a method for forming a resist pattern, comprising a step of applying a positive photoresist composition onto a substrate.

  ADVANTAGE OF THE INVENTION According to this invention, the positive photoresist composition suitable for the resist coating method by a discharge nozzle type, and the formation method of a resist pattern using the same are obtained.

Hereinafter, the present invention will be described in detail.
The “discharge nozzle type coating method” in the present specification is a method having a step of applying a positive photoresist composition to the entire coated surface of the substrate by relatively moving the discharge nozzle and the substrate. 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. Further, a method of adjusting the film thickness by applying a photoresist composition to the entire coated surface of the substrate in this way and then spinning the substrate is also included.
The “structural unit” in the present specification indicates a monomer unit constituting a polymer (resin).
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.

(A) Component The alkali-soluble novolak resin (A) used in the present invention can be arbitrarily selected from those that can be usually used as a film-forming substance in a positive photoresist composition.
In particular, when a material prepared so that the polystyrene-reduced mass average molecular weight of the entire component (A) (hereinafter referred to as only Mw) is 6000 or more is used, generation of streak-like marks in the discharge nozzle type coating method is caused. It is preferable at the point which can prevent more effectively. (A) The more preferable range of Mw of a component is about 6000-10000.

Specific examples of the alkali-soluble novolak resin (A) 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.

  In this invention, (A) component may consist of 1 type of novolak resin, and may consist of 2 or more types of novolak resins. When composed of two or more types of novolak resins, the Mw of each novolak resin is not particularly limited, but it is preferably prepared so that the Mw as a whole component (A) is in the range of 6000 or more.

(A1), (A2)
In the present invention, Mw synthesized by using formaldehyde as a condensing agent for the mixed phenols of m-cresol / p-cresol = 20/80 to 40/60 (preparation ratio) in the alkali-soluble novolak resin (A). Mw synthesized using formaldehyde as a condensing agent with respect to 4000 to 6000 novolak resin (A1) and mixed phenols of m-cresol / p-cresol = 20/80 to 40/60 (preparation ratio) is 5000 to It is 10,000 and it contains at least one kind of novolak resin selected from the novolak resins (A2) having a higher molecular weight than A1, and is suitable for the adjustment of a highly sensitive resist composition, and is not exposed to light. This is preferable from the viewpoint of improving the remaining film property of the part. In (A1) and (A2), the ratio of m-cresol / p-cresol 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. The monomer ratio of m-cresol structural unit / p-cresol structural unit in the finally obtained novolak resin is 25/75 to 45/55, particularly 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.
When at least one component (novolak resin) selected from the components (A1) and (A2) is used, the preferred content ratio of the components (A1) and (A2) in the component (A) is 10 to 60% by mass. More preferably, it is 45-55 mass%. When the content ratio of (A1) and (A2) in the component (A) is outside the above range, it is difficult to obtain an effect of increasing the sensitivity and the remaining film ratio.

(A3)
Moreover, Mw synthesize | combined using formaldehyde as a condensing agent with respect to mixed phenols of m-cresol / p-cresol = 50 / 50-70 / 30 (preparation ratio) to alkali-soluble novolak resin (A) is 9000 or more. It is preferable that the novolak resin (A3) is contained because it is excellent in the effect of suppressing the generation of streak-like marks. The ratio of m-cresol / p-cresol 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 monomer ratio of m-cresol structural unit / p-cresol structural unit in the finally obtained novolak resin is 55/45 to 75/25, particularly 60/40 to 70/30.
If the Mw of the component (A3) is too large, it may adversely affect the sensitivity of the resist composition and the releasability of the resist pattern in the resist pattern peeling step, and if it is too small, the effect of suppressing the generation of streak-like marks. 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.

Component (B) The positive photoresist composition of the present invention contains a phenolic hydroxyl group-containing compound (B) having a molecular weight of 1000 or less, thereby obtaining a sensitivity improvement effect. 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 (B) because high sensitivity can be achieved at a relatively low cost. In addition, when the component (B) is contained, a surface hardly-solubilized layer is strongly formed in the resist pattern, so that the amount of unremoved resist film at the time of development is small and development unevenness caused by the difference in development time occurs. It is suppressed and preferable.

When the molecular weight of the component (B) exceeds 1000, the sensitivity tends to decrease greatly, such being undesirable.
As the component (B), 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 following general formula (III). The phenolic hydroxyl group-containing compound is more preferable because it can effectively improve sensitivity.

[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 (IV):

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]
These may use any 1 type and may use 2 or more types together.

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

  (B) The compounding quantity of a component is 1-25 mass parts with respect to 100 mass parts of alkali-soluble novolak resin which is (A) component, Preferably the range of 5-20 mass parts is preferable. If the content of the component (B) in the photoresist composition is too small, the effect of improving the sensitivity and increasing the residual film ratio cannot be obtained sufficiently, 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.

(C) Component The (C) naphthoquinonediazide group-containing compound in the present invention is a photosensitive component. As this (C) 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 (C), an esterification reaction product of a phenolic hydroxyl group-containing compound represented by the following formula (II) 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.

As the component (C), other quinonediazide esterified products can be used in addition to the photosensitive component, but the amount used thereof is 30% by mass or less, particularly 25% by mass or less in the component (C). Preferably there is.
As other quinonediazide esterified products, for example, a phenolic hydroxyl group-containing compound represented by the general formula (III) and a 1,2-naphthoquinonediazidesulfonic acid compound, preferably a 1,2-naphthoquinonediazide-5-sulfonyl compound or preferably May be an esterification reaction product with a 1,2-naphthoquinonediazide-4-sulfonyl compound.

  The amount of component (C) in the photoresist composition of the present invention is 15 to 40 parts by mass, preferably 20 to 100 parts by mass of the total amount of the alkali-soluble novolak resin (A) and the phenolic hydroxyl group-containing compound (B). It is preferable to be within a range of ˜30 parts by mass. When the content of the component (C) 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.

(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 boiling point higher than that of PGMEA is used. By doing so, it is possible to prevent the phenomenon of streak marks after spinning under a relatively thin film condition with a coating film thickness of about 40 to 80 μm. 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 has a high effect of preventing the phenomenon of streak formation, and MBA is most preferable.
In the 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, under the thin film conditions of about 40 to 80 μm, streak marks after the spin are formed. The effect of suppressing the phenomenon that occurs 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.

Here, particularly in the field of manufacturing liquid crystal display elements, the thickness of the resist film formed on the glass substrate is usually 0.5 to 2.5 μm, more preferably 1.0 to 2.0 μm. For this purpose, it is preferable to adjust the film thickness by applying a photoresist composition on a substrate by a discharge nozzle method and then spinning the substrate.
In the present invention, the total amount of the components (A) to (C) in the photoresist composition using the organic solvent (D) is 30% by mass or less, preferably 20 to 20% based on the total mass of the composition. By preparing so that it may become 28 mass%, the favorable applicability | paintability at the time of discharging a photoresist composition from a discharge nozzle in strip shape and apply | coating on a board | substrate is acquired. In addition, since good fluidity can be obtained even if the film is subsequently spun, it is preferable for forming a resist film with good film thickness uniformity with high yield.

(E) component In this invention, it is preferable to make a photoresist composition contain surfactant (E). The content of the component (E) is preferably in the range of 900 ppm or less with respect to the entire photoresist composition in terms of effectively preventing the generation of streak-like marks.
There is no restriction | limiting in particular as surfactant (E), For example, the compound conventionally known as surfactant for resist can be used 1 type or 2 types or more.
As the surfactant (E), fluorine-silicon-based surface activity is preferable, and among them, nonionic fluorine-silicon-based surface activity in which perfluoroalkyl ester group, alkylsiloxane group, ethyleneoxy group, and propyleneoxy group are bonded. Agent (E-1) is preferred. Examples of the surfactant (E-1) include Megafac R-08 and R-60 (product name, manufactured by Dainippon Ink & Chemicals, Inc.).
Further, a surfactant component (E-2) having a fluorine content of 10 to 25% by mass and a silicon content of 3 to 10% by mass is more preferable, for example, X-70-090, X-70-091, X-70-092, X-70-093 (product name, manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. Since the effect which suppresses generation | occurrence | production is high, it is more preferable.
Furthermore, a polyester-modified polydialkylsiloxane-based surfactant (E-3) having a specific siloxane skeleton is also preferable, and examples thereof include BYK-310, BYK-315 (product, manufactured by BYK Chemie), and particularly BYK-310. Is more preferable because it can well suppress generation of haze, dripping marks, and streaks (streaks).
It is preferable that the total amount of the surfactants (E-1) to (E-3) occupy 50% by mass or more in the component (E). It may be 100% by mass.
Specific examples of surfactants other than the above (E-1) to (E-3) include surfactants for preventing striation, such as Florard FC-430, FC431 (product name, manufactured by Sumitomo 3M), Fluorosurfactants such as F-top EF122A, EF122B, EF122C, and EF126 (product name, manufactured by Tochem Products) are listed.

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 having such a configuration is suitable for a discharge nozzle type coating method, and prevents the formation of streak marks when the photoresist composition is discharged from the discharge nozzle in a strip shape and applied onto the substrate. Can do. In particular, when a photoresist composition is applied on a substrate and then the substrate is spun and the film thickness is adjusted to be thin (for example, about 0.5 to 2.5 μm), the thickness of the resist film is conventionally used. However, according to the photoresist composition of the present invention, the coating thickness before spinning is about 40 to 80 μm, preferably 60 μm. Even if it is formed to the extent, it is possible to prevent the occurrence of streak marks after spinning.

The photoresist composition of the present invention is also suitable for a method in which spin is not performed (spinless method) by applying the photoresist composition to the final required film thickness on the entire coated surface of the substrate by a discharge nozzle type coating method. In addition, it is also suitable for a method of adjusting the film thickness by applying a photoresist composition to the entire coated surface of the substrate and then spinning the substrate. Particularly suitable for the latter method, it is possible to prevent streak traces after spinning while suppressing the resist coating amount, thereby contributing to reduction in resist consumption, yield improvement, and cost reduction.

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 onto a substrate using a discharge nozzle type 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 spinless type TR63000S (product name; manufactured by Tokyo Ohka Kogyo Co., Ltd.) is known as a coating apparatus having the coating process.
Moreover, the said application | coating process can also use the means which spins a board | substrate and adjusts a film thickness thinly, after apply | coating a photoresist composition on a board | substrate by the discharge nozzle type coating method. As a coating apparatus having the coating process, a slit & spin type SK-1100G (product name; manufactured by Dainippon Screen Mfg. Co., Ltd.), a scan coating with MMN (multi-micro nozzle) + a spin type CL1200 (product name: Tokyo Electron) Co., Ltd.), TR63000F (product name; manufactured by Tokyo Ohka Kogyo Co., Ltd.) and the like are known.

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 the discharge nozzle type coating method is used, even if the substrate size and the apparatus size are increased, the resist is applied on the substrate without deteriorating the coating uniformity and the tact time. A film can be formed.
Moreover, the photoresist composition used is optimized for the discharge nozzle method, and it is possible to prevent the formation of streak-like marks on the photoresist film. In particular, when spin is performed after coating, the generation of streak-like marks can be prevented while suppressing the resist coating amount, which can contribute to a reduction in manufacturing cost.

Various physical properties of the positive photoresist composition were determined as follows.
(1) Evaluation of streaks:
Using a coating apparatus (product name TR63000F, manufactured by Tokyo Ohka Kogyo Co., Ltd.), a sample (positive photoresist composition) is coated on a glass substrate (1100 × 1250 mm ² ) on which a Cr film is formed (40 μm, 60 μm, 80 μm) and spin to form a coating film having a thickness of about 1.5 μm. The coating apparatus is configured to spin a substrate after coating a photoresist composition on the substrate by a discharge nozzle type coating method.
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 was observed was indicated as ◯, the case where faint was observed was indicated as Δ, and the case where it was greatly generated was indicated as ×.

(2) Confirmation of resist pattern forming ability:
A sample (positive photoresist composition) was applied with a film thickness of 50 μm onto a glass substrate (1100 × 1250 mm ² ) on which a Cr film was formed using a coating apparatus (manufactured by Tokyo Ohka Kogyo Co., Ltd., product name TR63000F). Then, a coating film having a film thickness of about 1.5 μm was formed by spinning.
Next, a resist film having a film thickness of 1.5 μm is formed in the same manner as the evaluation of the streak-like marks, and then a test chart mask (reticle) on which a mask pattern for reproducing a 3.0 μm line-and-space resist pattern is drawn. ) Through a mirror projection aligner MPA-600FA (manufactured by Canon; ghi line exposure apparatus). The exposure amount was 40 mJ / cm ² .
Subsequently, it was brought into contact with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution at 23 ° C. for 60 seconds, washed with water for 30 seconds, and spin-dried.

(Examples 1-7, Comparative Examples 1-2)
As examples and comparative examples, photoresist compositions were prepared with the formulations shown in Table 1 below, and streak-like marks were evaluated. The evaluation results are shown in Table 2 below. However, Example 1 is a reference example.
Further, in the evaluation of resist pattern forming ability, in each example, a 3.0 μm line-and-space resist pattern was reproduced according to the dimensions on the substrate. Due to the change, a dimensional change was observed in a part of the resist pattern.

As the component (A), the following (a1) to (a3) were used. (A) The compounding quantity of a component shall 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 the component (B), 10 parts by mass of the following (b1) was used.
(B1): Phenolic hydroxyl group-containing compound represented by the above formula (I) (M = 376)

As component (C), 29.7 parts by mass of the following (c1) or (c2) was used.
(C1): An esterification reaction product of 1 mol of the phenolic hydroxyl group-containing compound represented by the above formula (II) and 2.34 mol of 1,2-naphthoquinonediazide-5-sulfonyl chloride.
(C2): 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 (D) (organic solvent), 430 parts by mass of the following (d1) to (d3) were used.
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): X70-093 (product name, manufactured by Shin-Etsu Chemical Co., Ltd.)
As another component, 0.25 part by mass 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 (5)

Used in a discharge nozzle type coating method having a step of applying a positive photoresist composition to the entire coating surface of the substrate by relatively moving the discharge nozzle and the substrate, and having a size of 1000 × 1200 mm square or more. A positive photoresist composition applied to a glass substrate,
(A) an alkali-soluble novolak resin, (B) a phenolic hydroxyl group-containing compound having a molecular weight of 1000 or less, (C) a naphthoquinonediazide group-containing compound, and (D) an organic solvent,
The (D) organic solvent contains propylene glycol monomethyl ether acetate and an organic solvent having a boiling point higher than that of the propylene glycol monomethyl ether acetate ,
The high-boiling organic solvent is at least one selected from the group consisting of ethyl lactate and 3-methoxybutyl acetate, and
Wherein (D) the total amount of the organic solvent of the high boiling point of propylene glycol monomethyl ether acetate accounts for organic solvents, positive photoresist composition ejection nozzle type coating method, characterized in der Rukoto least 90 mass% . Discharge nozzle according to claim 1 Symbol placement, wherein the value of PGMEA / high-boiling organic solvent that represents the mass ratio of the organic solvent of the high boiling point and the propylene glycol monomethyl ether acetate is 10 / 1-1 / 1 -Type positive photoresist composition for coating method. 3. The method according to claim 1, wherein the discharge nozzle type coating method includes a step of spinning the substrate after coating a positive photoresist composition on the entire coated surface of the substrate. 4. A positive photoresist composition for a discharge nozzle type coating method. The positive for a discharge nozzle type coating method according to any one of claims 1 to 3 , wherein a positive photoresist composition is applied to the entire coating surface of the substrate by relatively moving the discharge nozzle and the substrate. A method for forming a resist pattern comprising a step of applying a type photoresist composition on a substrate. 5. The method of forming a resist pattern according to claim 4 , further comprising a step of spinning the substrate after applying a positive photoresist composition on the substrate.