KR20050031874A - Positive photoresist composition for discharge nozzle-coating method and formation method of resist pattern - Google Patents

Abstract

Provided is a positive photoresist composition containing particular surface active agent useful for preventing striped pattern scars while restricting amount of resist to be coated when the composition is applied on a substrate through discharge-nozzle. The photoresist composition comprises (A) alkali-soluble novolac resin, (C) naphthoquinone diazide group containing compound, (D) organic solvent and (E) surface active agent component having 10-25 wt.% of fluorine and 3-10 wt.% of silicon. The composition further includes (B) phenol hydroxy group containing compound having 1000 or less of molecular weight. The discharge-nozzle coating method comprises moving the discharge nozzle and a substrate relative to each other to paint overall area of the substrate. The (a) component has a mass average molecular weight Mw of at least 6000 in terms of polystyrene.

Description

POSITIVE PHOTORESIST COMPOSITION FOR DISCHARGE NOZZLE-COATING METHOD AND FORMATION METHOD OF RESIST PATTERN}

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

Conventionally, in the manufacturing field of the liquid crystal display element using a small glass substrate, the method of spin after center dripping is used as a resist coating method (following nonpatent literature 1).

In the coating method which spins after center dropping, favorable coating uniformity can be obtained, but, for example, in the case of a 1 m x 1 m large substrate, the amount of resist that is thrown out during rotation (spinning) and discarded is considerably increased. In addition, there is a problem in breaking the substrate due to the high speed rotation and securing the tact time. In addition, since the coating performance in the method of spin after center dripping depends on the rotational speed at the time of spin and the coating amount of the resist, it is applied to the fifth generation substrate (1000 mm x 1200 mm to 1280 mm x 1400 mm) which is larger in size. There is a problem that there is no general-purpose motor that can achieve the required acceleration, and that special orders of such motors increase component costs.

In addition, even if the substrate size and the device size are enlarged, the required performance in the coating process hardly changes, for example, coating uniformity ± 3% and tact time 60 to 70 seconds / sheet. As a result, it has become difficult to cope with demands other than coating uniformity.

From this phenomenon, a resist coating method by a discharge nozzle type has been proposed as a new resist coating method that can be applied to large-sized substrates after the fourth generation substrate (680 mm x 880 mm), particularly after the fifth generation substrate.

The resist coating method by a discharge nozzle type is a method of apply | coating a positive photoresist composition to the whole application | coating surface of a board | substrate by moving a discharge nozzle and a board | substrate relatively, for example, a some nozzle hole heats. A method of using a discharge nozzle having a discharge or slit discharge port arranged in a shape and capable of discharging the photoresist composition in a band shape has been proposed. Moreover, after apply | coating a photoresist composition to the whole application | coating surface of a board | substrate by a discharge nozzle type, the method of adjusting the film thickness by spinning the board | substrate is also proposed.

(Non-Patent Document 1) Electronic Journal August 2002, pages 121-123.

Regarding the ejection nozzle type coating method, a suitable coating device has been developed and published recently, and the adaptation of the photoresist composition used in such a coating method has become an important problem in the future.

This invention is made | formed in view of the said situation, and an object of this invention is to provide the positive photoresist composition which can be used suitably for a discharge nozzle type coating method, and the method of forming the resist pattern using the same.

MEANS TO SOLVE THE PROBLEM The present inventors newly discovered that when a photoresist composition was apply | coated to the whole application | coating surface of a board | substrate by the ejection nozzle type | mold coating method, the stripe-shaped damage may be formed in a coating film. Moreover, especially when a board | substrate was spun, it turned out that stripe-shaped flaw is easy to form in the center part of a board | substrate. In addition, it has been found that the occurrence of streaked scratches can be suppressed by forming a thick coating film before spin, but since the coating amount of the resist is increased, particularly, the resist consumption is strictly suppressed (resist saving). It is difficult to apply in the manufacture field of the recent liquid crystal display element which is required.

Therefore, as a result of further studies, when the photoresist composition contains a specific surfactant, when the photoresist composition is discharged from the discharge nozzle and applied onto the substrate, streaked scratches are preferably generated while suppressing the resist coating amount. It has been found that can be prevented to complete the present invention.

That is, the positive photoresist composition of the present invention is used in a discharge nozzle type coating method having a process of applying the positive photoresist composition to the entire application surface of the substrate by moving the discharge nozzle and the substrate relatively. ) Interfaces having an alkali-soluble novolak resin, (C) a naphthoquinone diazide group-containing compound, (D) an organic solvent, and (E) a fluorine content of 10 to 25 mass% and a silicon content of 3 to 10 mass%. It is characterized by containing an active ingredient.

Moreover, this invention uses the discharge nozzle type | mold coating method which apply | coats a positive photoresist composition to the whole application | coating surface of a board | substrate by moving a discharge nozzle and a board | substrate relatively, and the positive type photoresist for the discharge nozzle type | mold coating method of this invention. It has a process of apply | coating a composition on a board | substrate, The method of forming the resist pattern characterized by the above-mentioned.

The "discharge nozzle type coating method" in this specification is a method which has a process of apply | coating a positive photoresist composition to the whole application | coating surface of a board | substrate by moving a discharge nozzle and a board | substrate relatively, specifically, several There exists a method of using the nozzle which has a discharge opening in which the nozzle hole was arranged in the form of a row, the method of using the nozzle which has a slit-shaped discharge opening, etc. are mentioned. Moreover, after apply | coating a photoresist composition to the whole coating surface of a board | substrate in this way, the method of adjusting the film thickness by spinning the board | substrate is also included.

The "structural unit" in this specification shows the monomeric unit which comprises a polymer (resin).

In this specification, the "coating surface of a board | substrate" refers to the area | region to which the resist composition is apply | coated in a board | substrate, and is generally one side of a board | substrate.

Best Mode for Carrying Out the Invention

Hereinafter, the present invention will be described in detail.

[(A) component]

Alkali-soluble novolak resin (A) used by this invention can be arbitrarily selected and used from what can be normally used as a film formation material in positive type photoresist composition.

In particular, when the polystyrene reduced mass average molecular weight (hereinafter, referred to only as Mw) of the entire component (A) is 6000 or more, it is preferable in that the occurrence of streaked scratches in the ejection nozzle type coating method can be more effectively prevented. The more preferable range of Mw of (A) component is about 6000-10000.

As a specific example of alkali-soluble novolak resin (A), the novolak resin etc. which are obtained by making the phenols illustrated below and the aldehydes illustrated below react with an acidic catalyst etc. are mentioned.

As said phenols, For example, Phenol; cresols such as m-cresol, p-cresol and o-cresol; Xylenols such as 2,3-xylenol, 2,5-xylenol, 3,5-xylenol and 3,4-xylenol; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2- alkyl phenols such as tert-butylphenol, 2-tert-butyl-4-methylphenol and 2-tert-butyl-5-methylphenol; alkoxyphenols such as p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol and m-propoxyphenol; isopropenylphenols such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol and 2-ethyl-4-isopropenylphenol; Arylphenols such as phenylphenol; And polyhydroxyphenols such as 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone and pyrogallol. These may be used independently and may be used in combination of 2 or more type. Among these phenols, m-cresol and p-cresol are particularly preferable.

Examples of the aldehydes include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butylaldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanealdehyde, furfural, furylaldehyde, benzaldehyde, and benzaldehyde. Aldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde , o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamon aldehyde and the like. These may be used independently and may be used in combination of 2 or more type. Among these aldehydes, formaldehyde is preferable in view of easy availability.

As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, oxalic acid, paratoluenesulfonic 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 resin. When it consists of two or more types of novolak resins, although Mw of each novolak resin is not specifically limited, It is preferable to prepare so that Mw may be 6000 or more as the whole (A) component.

[(A ') component]

In the present invention, formaldehyde is used as a condensing agent for the mixed phenols of (A ') m-cresol / p-cresol = 20/80 to 40/60 (injection ratio) in the alkali-soluble novolak resin (A). Containing at least one member selected from the group consisting of novolak resins having a Mw of from 4000 to 10,000 is suitable for the preparation of a highly sensitive resist composition, and the residual film properties of the unexposed parts are improved. Preferred at

In particular, the novolak resin (A1) which has Mw of 4000-6000 synthesize | combined using m-cresol / p-cresol = 20 / 80-40 / 60 (injection ratio) using formaldehyde as a condensing agent, m-cresol / p-cresol = 20/80 to 40/60 (injection ratio), novolac having a Mw of 5000 to 10000 synthesized using formaldehyde as a condensing agent and having a larger Mw than (A1) It is preferable that resin (A2) is contained in (A) component.

The Mw of the components (A1) and (A2) is preferably Mw of 4000 to 6000, particularly 4500 to 5500, and the latter (A2) of the former (A1) from the viewpoint of increasing the sensitivity of the resist composition and improving the residual film ratio. It is preferable that it is 5000-10000, especially 5500-6500.

In the above (A '), the ratio of m-cresol / p-cresol is particularly preferably 25/75 to 35/65. In addition, a part of p-cresol used in the reaction is present in the reaction system as an unreacted substance or a binary nucleus, and is removed at the fractionation operation for the purpose of cutting the low molecular weight material which is carried out after the completion of the synthesis reaction. The monomer ratio of the m-cresol structural unit / p-cresol structural unit in resin becomes 25/75-45/55, especially 30/70-40/60.

The preferable content rate of the sum total of (A ') component in (A) component is 10-60 mass%, More preferably, it is 45-55 mass%. If the content ratio of (A ') component in (A) component is out of the said range, it will be hard to obtain the effect of high sensitivity and a residual film ratio improvement.

[(A3) component]

Moreover, Mw synthesize | combined using formaldehyde as a condensing agent with respect to mixed phenols of m-cresol / p-cresol = 50 / 50-70 / 30 (injection ratio) to alkali-soluble novolak resin (A) is 9000 or more It is preferable to contain novolak resin (A3) from the point which is excellent in the effect which suppresses generation | occurrence | production of a stripe-shaped flaw. The ratio of m-cresol / p-cresol is particularly preferably 55/45 to 65/35. In addition, a part of p-cresol used in the reaction is present in the reaction system as an unreacted substance or a binary nucleus, and is removed at the fractionation operation for the purpose of cutting the low molecular weight material which is carried out after the completion of the synthesis reaction. The monomer ratio of the m-cresol structural unit / p-cresol structural unit in resin becomes 55/45-75/25, especially 60/40-70/30.

If Mw of the component (A3) is too large, the sensitivity of the resist composition may be adversely affected or adversely affect the peelability of the resist pattern in the resist pattern stripping step. , Mw is preferably 9000 or more, and more preferably 9500 to 15000.

When using (A3) component, 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, there is a possibility that the sensitivity of the resist composition may be adversely affected or the peelability of the resist pattern in the resist pattern peeling step may be adversely affected. There is a lack of inhibitory effect.

In this invention, it is preferable that (A) component contains both of said (A ') component and (A3) component. In this case, the content ratio of the component (A ') and the component (A3) is preferably in the range of (A') / (A3) = 10/90 to 60/40 by mass ratio, and in the range of 45/55 to 55/45. I am more preferred. Moreover, it is further more preferable that (A) component contains three types of said (A1) component, (A2) component, and (A3) component.

Moreover, if desired, (A) component can also contain novolak resins other than (A ') and (A3). The preferable content rate of the sum total of (A ') and (A3) in (A) component is 50 mass% or more, More preferably, it is 90 mass% or more. 100 mass% may be sufficient.

[(B) component]

The positive photoresist composition of this invention can obtain a sensitivity improvement effect by containing the phenolic hydroxyl group containing compound (B) whose molecular weight is 1000 or less. In particular, in the field of liquid crystal display element manufacturing, the improvement of throughput is a very big problem and the resist consumption tends to be increased. Therefore, a high sensitivity and a low cost are required in the photoresist composition. It is preferable because high sensitivity can be achieved relatively inexpensively. In addition, when the component (B) is contained, the surface poorly soluble layer is strongly formed in the resist pattern, so that the amount of film reduction of the resist film in the unexposed portion is small at the time of development, and the occurrence of developmental unevenness caused by the difference in development time is suppressed. Is preferred.

When the molecular weight of (B) component exceeds 1000, since the fall of a sensitivity tends to become large, it is not preferable.

As this (B) component, the phenolic hydroxyl group containing compound of the molecular weight 1000 or less conventionally used for the positive photoresist composition for liquid crystal display element manufacture can be used suitably. Especially, since the phenolic hydroxyl group containing compound represented by following General formula (III) can improve a sensitivity effectively, it is more preferable.

[Wherein, R ¹ to R ⁸ each independently represent 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 ¹⁰ and R ¹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ⁹ may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, in which case Q is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a residue represented by the following formula (IV)

Wherein R ¹² and R ¹³ each independently represent 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 is Represents an integer of 1 to 3); Or Q is and R ⁹ together with the carbon atoms between Q and R ⁹ represents a cycloalkyl group having 3 to 6 carbon atoms; a and b represent the integer of 1-3; d represents an integer of 0 to 3; when a, b or d is 3, R ³ , R ⁶ or R ⁸ are not present; n represents an integer of 0 to 3]

Any one of these may be used, or 2 or more types may be used together.

Among the phenolic hydroxyl group-containing compounds exemplified above, the compound represented by the following formula (I) is particularly preferable because of its high sensitivity and high residual film ratio.

    As for the compounding quantity of (B) component, 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. When the content of the component (B) in the photoresist composition is too small, the effect of improving sensitivity and high residual film ratio cannot be sufficiently obtained, and when too large, residues are likely to occur on the surface of the substrate after development, and the raw material cost becomes expensive. Because it is not desirable.

[(C) component]

The (C) naphthoquinone diazide group containing compound in this invention is a photosensitive component. As this (C) component, what has conventionally been used as the photosensitive component of the positive photoresist composition for liquid crystal display element manufacture can be used.

For example, the esterification product of the phenolic hydroxyl group containing compound and 1,2-naphthoquinone diazide sulfonic-acid compound represented by following formula (II) especially as (C) component is very cheap and highly sensitive photoresist. It is preferable at the point that a 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%, there is a problem in that the film reduction after development is likely to occur, and the residual film ratio is low.

The 1,2-naphthoquinone diazide sulfonic acid compound is preferably a 1,2-naphthoquinone diazide-5-sulfonyl compound.

Moreover, although the quinone diazide ester compound can be used for component (C) other than the said photosensitive component, it is preferable that these usage-amounts are 50 mass% or less, especially 25 mass% or less in (C) component.

As another quinone diazide ester compound, For example, the phenolic hydroxyl group containing compound represented by the said General formula (III), and 1,2-naphthoquinone diazide sulfonic-acid compound, Preferably 1,2-naphthoquinone Esterification reaction products of diazide-5-sulfonyl compounds or preferably 1,2-naphthoquinonediazide-4-sulfonyl compounds can be used.

The compounding quantity of (C) component in the photoresist composition of this invention is 15-40 mass with respect to 100 mass parts of total amounts of alkali-soluble novolak resin (A) and the phenolic hydroxyl group containing compound (B) mix | blended as needed. It is preferable to carry out in the range of 20-30 mass parts preferably. When content of (C) component is less than the said range, the fall of transferability will become large and a resist pattern of a desired shape will not be formed. On the other hand, when more than the said range, a sensitivity and resolution will deteriorate and a residue will become easy to generate | occur | produce after image development processing.

[(D) component]

It is preferable that the composition of this invention dissolves (A)-(C) component, (E) component, and various addition components in the organic solvent (D), and uses it in solution form.

As the organic solvent used in the present invention, propylene glycol monomethyl ether acetate (PGMEA) is preferred because it is excellent in coating property and excellent in film thickness uniformity on a resistive coating even on a large glass substrate.

Although it is most preferable to use PGMEA as a sole solvent, solvent other than PGMEA can also be used together, For example, ethyl lactate, (gamma) -butyrolactone, a propylene glycol monobutyl ether, etc. are mentioned.

When ethyl lactate is used, it is preferable to mix | blend in the range of 0.1-10 times by mass with respect to PGMEA, Preferably it is 1-5 times. In addition, when using (gamma) -butyrolactone, it is preferable to mix | blend in the range of 0.01-1 time, preferably 0.05-0.5 time by mass ratio with respect to PGMEA.

Especially in the field of liquid crystal display element manufacture, the thickness of the resist film formed on a glass substrate needs to be 0.5-2.5 micrometers normally, More preferably, 1.0-2.0 micrometers, In order to do this, the photoresist on a board | substrate is carried out by a discharge nozzle method. After apply | coating a composition, it is preferable to spin the board | substrate and to adjust a film thickness.

In this invention, the total amount of the said (A)-(C) component in a photoresist composition using an organic solvent (D) is 30 mass% or less with respect to the total mass of a composition, Preferably it is 20-28 mass% More preferably, it is prepared to be 10 to 25% by mass, whereby the photoresist composition is discharged in a band shape from the discharge nozzle to obtain good applicability when applied onto the substrate, and at the same time, good fluidity when spun afterwards. It is preferable to form a resist film having a good film thickness uniformity in high yield because it can be obtained.

[(E) component]

The fluorine content in surfactant (E) component is a numerical value calculated | required by ion chromatography after forming fluorine ion. In addition, silicon content is a numerical value calculated by inductively coupled plasma emission spectrometry (ICP).

More specifically, the fluorine content is determined by ion chromatography after heating the sample in an electric furnace to burn carbon and hydrogen to generate fluorine ions. In addition, silicon content prepares a sample by solid or a solution, and quantifies by an ICP method.

In this invention, the fluorine content of (E) component is 10-25 mass%, More preferably, it is 15-25 mass%, and silicon content is 3-10 mass%, More preferably, it is 5-10 mass%. . It is preferable that the fluorine content with respect to the silicon content in (E) component is 2 to 5 times. By containing the surfactant whose fluorine content and silicon content exist in the said range in a photoresist composition, generation | occurrence | production of the stripe-shaped flaw in the ejection nozzle type coating method can be prevented effectively.

(E) component will not be specifically limited if it satisfy | fills the fluorine content and silicon content of the said range, As a preferable specific example, brand name X-70-090, X-70-091, X-70-092, X-70- And nonionic fluorine-silicone surfactants in which a perfluoroalkyl group such as 093 (all manufactured by Shin-Etsu Chemical Co., Ltd.) and an alkylsiloxane group and an alkyleneoxy group are bonded. As for the specific example here, all are 21 mass% of fluorine content, and 7 mass% of silicon content.

Especially among these, X-70-093 is more preferable, even if a small amount of resist dropping is high because it has a high effect of suppressing occurrence of streaked scratches and dry unevenness.

The amount of the component (E) is 0.001 with respect to the solid content excluding the organic solvents (D) and (E) in the photoresist composition in order to effectively and efficiently prevent the generation of streaked scratches in the ejection nozzle type coating method. 1 mass%, Preferably it is desirable to set it as 0.01-0.5 mass%.

[Other Ingredients]

Various additives, such as a storage stabilizer, can be used for the composition of this invention in the range which does not impair the objective of this invention further.

UV absorbers for anti-halation, for example 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-di Ethyl amino azobenzene, curcumin, etc. can be contained suitably.

Moreover, the adhesive improving agent for improving the adhesiveness of the layer which consists of a photoresist composition, and its lower layer can be contained suitably. As an adhesive improving agent, 2- (2-hydroxyethyl) pyridine is preferable, and when it contains suitably in a photoresist composition, for example, when forming a resist pattern on metal films, such as a Cr film, it consists of a photoresist composition. The adhesiveness of a layer and a metal film can be improved effectively.

In the case where the adhesion improving agent is contained, if the blending amount is too large, the change in the resist composition tends to deteriorate. If the adhesion improving agent is too small, the effect of improving the adhesion may not be sufficiently obtained, so that it is within the range of 0.1 to 10% by mass based on the total solids. It is preferable.

The photoresist composition having such a configuration is suitable for the coating method of the discharge nozzle method, and can prevent streaked scratches from occurring when the photoresist composition is discharged in a band shape from the discharge nozzle and applied onto the substrate. In particular, when the photoresist composition is applied (liquid stacked) on the substrate, and then the substrate is spun to adjust the film thickness to be thin (for example, about 0.5 to 2.5 µm), the coating thickness of the resist film is adjusted to 300 to 500. Stripe-like scratches were more likely to occur after spin unless they were formed thicker than about µm. According to the photoresist composition according to the present invention, the stripe-shaped stripe after spin is formed even if the coating thickness before spin is formed at about 80 to 120 µm, preferably about 100 µm. Scratches can be prevented.

The photoresist composition of the present invention is also suitable for a method (spinless method) in which the photoresist composition is finally applied to the entire film coated surface of the substrate by the ejection nozzle type coating method at the required film thickness and is not spun. After apply | coating a photoresist composition to the whole, it is also suitable for the method of adjusting a film thickness by spinning a board | substrate. Particularly suitable for the latter method, it is possible to prevent streaked scratches after spin while suppressing the resist coating amount, thereby contributing to reduction of resist consumption, productivity improvement and cost reduction.

[Formation method of resist pattern]

EMBODIMENT OF THE INVENTION Hereinafter, one Embodiment of the formation method of the resist pattern of this invention is described.

The formation method of the resist pattern of this invention has the process of apply | coating the positive photoresist composition of this invention on a board | substrate using a discharge nozzle type coating method. This application | coating process can be performed with the apparatus provided with the means which moves a discharge nozzle and a board | substrate relatively. The discharge nozzle may be configured so that the photoresist composition discharged here is applied in a band shape on the substrate, but is not particularly limited, but, for example, a discharge nozzle having a discharge port in which a plurality of nozzle holes are arranged in a column shape, or a slit A discharge nozzle having a discharge port in the shape can be used. As a coating apparatus which has this coating process, TR63000S (product name; manufactured by Toyo Kogyo Co., Ltd.) of a coat and a spinless system is known.

Moreover, in the said application | coating process, after apply | coating a photoresist composition on a board | substrate by a discharge nozzle type coating method, you may use the means which spins a board | substrate and adjusts a film thickness thinly. Examples of the coating device having the coating step include a slit and spin type SK-1100G (product name; manufactured by Dainippon Screen Seizo Co., Ltd.) and CL1200 (product name; spin type) using MMN (multi micro nozzle). Tokyo Electron Co., Ltd., a TR63000F (product name; manufactured by Toyo Kogyo Kogyo Co., Ltd.) of a coat and a spin system are known.

In this way, the well-known method can be used suitably for the process for forming a resist pattern after apply | coating a positive photoresist composition to the whole coated surface of a board | substrate.

For example, the substrate on which the photoresist composition is applied is heated and dried (prebaked) at about 100 to 140 ° C to form a resist film. Thereafter, the resist film is subjected to selective exposure through a desired mask pattern. The wavelength at the time of exposure can use ghi line (g line, h line, and i line) or i line preferably, and uses a suitable light source, respectively.

Thereafter, the development treatment is carried out using a developer composed of an alkaline aqueous solution, for example, an aqueous solution of 1 to 10% by mass of tetramethylammonium hydroxide (TMAH), to the resist film after selective exposure.

As a method of bringing a developer into contact with the resist film, for example, a method of stacking the liquid from one end to the other of the substrate, or spreading the developer evenly over the entire surface of the substrate from a developer dropping nozzle provided near the center of the substrate. Method can be used.

After developing for about 50 to 60 seconds and developing, a resist pattern can be obtained by performing a rinsing step of washing off the developer remaining on the resist pattern surface using a rinse solution such as pure water.

According to the formation method of such a resist pattern, since the ejection nozzle type | mold coating method is used, even if a board | substrate size and apparatus size become large, a resist film can be formed on a board | substrate without degrading application | coating uniformity and tact time.

In addition, the photoresist composition to be used is adapted to the discharge nozzle method, and the generation of streaked scratches on the photoresist film is prevented. In particular, in the case of spin after coating, the generation of streaked scratches can be prevented while suppressing the amount of resist coating, which can contribute to a reduction in manufacturing cost.

Moreover, although Unexamined-Japanese-Patent No. 2000-181055 exists as a prior art regarding the technique regarding the nonionic fluorine-silicone type surfactant which (E) component of this invention belongs, there is no description regarding a discharge nozzle type coating method. .

EXAMPLE

The overall physical properties of the positive photoresist composition were determined by the following method.

(1) Evaluation of stripe scratches:

A predetermined thickness (80 μm, 100 μm, 120 μm) was applied onto a glass substrate (1100 mm × 1250 mm) on which a Cr film was formed using a sample (positive photoresist composition) using a coating apparatus (manufactured by Tokyo Kogyo Co., Ltd., product name TR63000F). After laminating | stacking a liquid, it spins and formed the coating film of about 1.5 micrometers in film thickness. The coating device is configured to spin the substrate after applying the photoresist composition onto the substrate by a discharge nozzle type coating method.

Subsequently, the temperature of the hot plate was set to 130 ° C., and the first drying was performed for 60 seconds by a proximity bake with an interval of about 1 mm. Then, the temperature of the hot plate was set to 120 ° C., and the interval of 0.5 mm was Second drying was performed for 60 seconds by a dull proximity baking to form a resist film having a thickness of 1.5 m.

 The surface of the obtained resist film was observed under a sodium lamp, and the occurrence of streaked scratches was not seen, and the appearance of faint △, and the large occurrence were shown in the table as x.

(2) Confirmation of resist pattern forming ability:

The sample (positive photoresist composition) was deposited on a glass substrate (1100 mm x 1250 mm) on which a Cr film was formed using a coating apparatus (manufactured by Tokyo Kogyo Co., Ltd., product name TR63000F) at a thickness of 100 µm, and spin-coated. A coating film having a thickness of about 1.5 mu m was formed.

Subsequently, a resist film having a thickness of 1.5 μm was formed by the same method as the above-described stripe scratch evaluation, and then mirror projection was performed through a test chart mask (reticle) having a mask pattern for reproducing a resist pattern of 3.0 μm line and space. Exposure was carried out using the aligner MPA-600FA (manufactured by Canon Corporation; ghi line exposure apparatus). The exposure amount was 40 mJ / cm ² .

It was then contacted with 23 ° C., 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, washed with water for 30 seconds, and then spin dried.

(Examples 1 to 3, Comparative Example 1)

As an Example and a comparative example, the photoresist composition was prepared by the compounding shown in following Table 1, and the stripe-shaped flaw was evaluated. The evaluation results are shown in Table 2 below.

In the evaluation of the resist pattern formation ability, all of the Examples reproduced the resist pattern of 3.0 µm line and space on the substrate in the dimension, but in the Comparative Example, part of the resist pattern was caused by the change in the film thickness due to the effect of streaked scratches. The dimensional change was confirmed.

As the component (A), the following (a1) to (a3) were used. The compounding quantity of (A) component is 100 mass parts. In Table 1, (//) has shown that it was a mixture mixed by the mass ratio described there.

(a1): Novolak resin obtained by condensation-reaction by the conventional method using formaldehyde as a condensing agent and a oxalic acid catalyst with respect to the mixed phenols of m-cresol / p-cresol = 30/70, water-methanol mixing The novolak resin of Mw 5000 obtained by fractionating with a solvent.

(a2): Water-methanol mixed with the novolak resin obtained by carrying out condensation reaction by the conventional method using formaldehyde as a condensing agent and the oxalic acid catalyst with respect to the mixed phenols of m-cresol / p-cresol = 30/70. The novolak resin of Mw 6300 obtained by fractionating with a solvent.

(a3): Novolak resin obtained by condensation-reaction by the conventional method using formaldehyde as a condensing agent and the oxalic acid catalyst with respect to the mixed phenols of m-cresol / p-cresol = 60/40 is mixed with water-methanol A novolak resin of Mw 11000 obtained by fractionating with a solvent.

As the component (B), 10 parts by mass of the following (b1) was used.

(b1): The phenolic hydroxyl group containing compound represented by the said Formula (I) (molecular weight = 376).

As the component (C), 29.7 parts by mass of the following (c1) or (c2) was used.

(c1): The esterification reaction product of 1 mol of phenolic hydroxyl group containing compounds represented by said Formula (II), and 2.34 mol of 1,2-naphthoquinone diazide-5-sulfonyl chlorides.

(c2): 1 mol of bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) -3,4-dihydroxyphenylmethane and 1,2-naphthoquinonediazide-5-sulfonylchloride 2.11 Molar esterification reaction product.

430 mass parts of following (d1) was used as (D) component (organic solvent).

(d1): PGMEA.

As the component (E) (surfactant), the following (e1) to (e3) were used in the formulation of Table 1.

(e1) X-70-093 (made by Shin-Etsu Chemical Co., Ltd., fluorine content 21 mass%, silicon content 7.0 mass%).

(e2) X-70-090 (made by Shin-Etsu Chemical Co., Ltd., fluorine content 18 mass%, silicon content 6 mass%).

(e3) Megapak R-60 (Dainippon Ink Co., Ltd. make, 8 mass% of fluorine content, 2 mass% of silicon content).

As other components, 0.25 parts by mass of 2- (2-hydroxyethyl) pyridine was used based on the total solids.

After dissolving the said (A)-(D) component and other components uniformly, 0.05 mass% of surfactant (E) is added with respect to the total solid except (D), and this is used the membrane filter of 0.2 micrometer of pore diameters. And filtration to prepare a positive photoresist composition.

(A) (mixing ratio) (Mw) (B) (C) (mixed ratio) (D) (E) Example 1 a1 / a2 / a3 (2/3/5) (8000) b1 c1 d1 e1 Example 2 Same as above Same as above Same as above Same as above e2 Example 3 Same as above Same as above c1 / c2 (1/1) Same as above e1 Comparative Example 1 Same as above Same as above c1 Same as above e3

Evaluation of Striped Scratches 80㎛ 100 μm 120 μm Example 1 ○ ○ ○ Example 2 ○ ○ ○ Example 3 ○ ○ ○ Comparative Example 1  × △ △

According to this invention, the positive photoresist composition suitable for the resist coating method by a discharge nozzle type, and the formation method of the resist pattern using the same can be obtained.

Claims (13)

A positive photoresist composition for use in a discharge nozzle type coating method having a process of applying a positive photoresist composition to the entire application surface of a substrate by moving the discharge nozzle and the substrate relatively, (A) Alkali-soluble novolac resin , (C) a naphthoquinone diazide group-containing compound, (D) an organic solvent, and (E) a surfactant component having a fluorine content of 10 to 25 mass% and a silicon content of 3 to 10 mass%. A positive photoresist composition for a discharge nozzle type coating method, characterized in that. The positive type photoresist composition for a discharge nozzle type coating method according to claim 1, further comprising (B) a phenolic hydroxyl group-containing compound having a molecular weight of 1000 or less. The positive photoresist composition for a discharge nozzle type coating method according to claim 1, wherein the polystyrene reduced mass average molecular weight (Mw) of the component (A) is 6000 or more. The said (A) component is synthesize | combined using formaldehyde as a condensing agent with respect to the mixed phenols of (A ') m-cresol / p-cresol = 20 / 80-40 / 60 (injection ratio). A positive photoresist composition for a discharge nozzle type coating method, characterized by containing at least one member selected from the group consisting of novolac resins having a Mw of 4000 to 10,000. The Mw according to claim 1, wherein the component (A) is synthesized using m-cresol / p-cresol = 50/50 to 70/30 (injection ratio) of mixed phenols using formaldehyde as a condensing agent. The novolak resin (A3) which is above is contained, The positive type photoresist composition for discharge nozzle type coating methods characterized by the above-mentioned. The Mw according to claim 5, wherein the component (A) is synthesized using m-cresol / p-cresol = 20/80 to 40/60 (injection ratio) of mixed phenols using formaldehyde as a condensing agent. Mass ratio of content of the (A ') component and content of the said (A3) component containing the (A') component which is 1 or more types chosen from the group which consists of -10000 novolak resin, and the said (A3) component. A positive photoresist composition for a discharge nozzle type coating method, wherein the value of (A ') / (A3) is 10/90 to 60/40. The positive type photoresist composition for a discharge nozzle type coating method according to claim 2, wherein the component (B) contains a phenolic hydroxyl group-containing compound represented by the following formula (I). The said (C) component contains the esterification reaction product of the phenolic hydroxyl group containing compound and 1,2-naphthoquinone diazide sulfonic-acid compound represented by following formula (II), The said (C) component characterized by the above-mentioned. Positive photoresist composition for a discharge nozzle type coating method. The positive type photoresist composition for a discharge nozzle type coating method according to claim 1, wherein the component (D) contains propylene glycol monomethyl ether acetate. The positive type photoresist composition for a discharge nozzle type coating method according to claim 1, further comprising 2- (2-hydroxyethyl) pyridine. The positive type photo for discharge nozzle type coating method according to claim 1, wherein the discharge nozzle type coating method has a step of spinning the substrate after applying the positive type photoresist composition to the entire application surface of the substrate. Resist composition. A method of applying a positive photoresist composition to an entire application surface of a substrate by moving a discharge nozzle and a substrate relatively, comprising a process of applying the positive photoresist composition according to claim 1 on a substrate. How to form a pattern. The method of forming a resist pattern according to claim 12, further comprising a step of spinning the substrate after applying a positive photoresist composition on the substrate.