KR100619520B1 - Positive photoresist composition for discharge nozzle type application and resist pattern formation method - Google Patents

Abstract

A positive photoresist composition used 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) a polystyrene equivalent mass average molecular weight ( A positive photoresist composition for a discharge nozzle type coating method comprising Mw) an alkali-soluble novolak resin having a 6000 or more, a (C) naphthoquinone diazide group-containing compound, and (D) an organic solvent.

Description

Positive photoresist composition and method for forming resist pattern for discharge nozzle coating method {POSITIVE PHOTORESIST COMPOSITION FOR DISCHARGE NOZZLE TYPE APPLICATION AND RESIST PATTERN FORMATION METHOD}

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 field of manufacturing a liquid crystal display element using a small glass substrate, as a resist coating method, a method of dropping a resist composition in the center of the substrate and then spinning was used (Non-Patent Document 1).

In the coating method that spins after the central dropping, good coating uniformity is obtained. However, in the case of a large substrate of 1 m × 1 m class, for example, a large amount of resist that is thrown away during spin (spinning) and discarded becomes large, Problems such as cracking of the substrate and securing of tact time due to rotation occur. 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, the fifth generation substrate (about 1000 mm x 1200 mm to 1280 mm x 1400 mm) to be further enlarged is applied. There was a problem that there was no general-purpose motor to obtain the required acceleration, and that the special cost of such a motor increased the parts cost.

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. In this case, it has become difficult to cope with demands other than coating uniformity.

From this phenomenon, a resist coating method using a discharge nozzle type has been proposed as a new resist coating method that can be applied to a large substrate 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 surface of the application | coating surface of a board | substrate by moving a discharge nozzle and a board | substrate relatively. As this method, for example, a method of using a discharge nozzle having a discharge or slit discharge port arranged in a shape in which a plurality of nozzle holes are arranged and capable of discharging the photoresist composition in a band shape has been proposed. Moreover, after apply | coating a photoresist composition to the whole surface of the application | coating surface of a board | substrate by a discharge nozzle type, the method of adjusting this film thickness by spinning this 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 recently been developed and published, and the adaptation of the photoresist composition used in the coating method related thereto 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 type photoresist composition which can be used suitably for a discharge nozzle type coating method, and the formation method of the resist pattern using the same.

The present inventors newly discovered that after the photoresist composition was applied to the entire coated surface of the substrate by the ejection nozzle type coating method, streaks of streaks were formed on the coating film. Moreover, especially when a board | substrate was spun, it discovered that the trace of stripe pattern is easy to form in the center part of a board | substrate. In addition, it has been found that the generation of the stripe traces can be suppressed by forming the coating film thickness before the spin thickly. However, since the coating amount of the resist is increased, it is particularly strict to reduce the resist consumption (resist saving). Practical use is difficult in the recent liquid crystal display element manufacturing field required.

Therefore, as a result of further studies, it is preferable to discharge a photoresist composition from a discharge nozzle and apply it onto a substrate by using a novolak resin having a polystyrene reduced mass mean molecular weight (Mw) of 6000 or more as the alkali-soluble resin component. It has been found that the generation of streaked traces can be prevented while suppressing the amount of resist coating, and the present invention has been completed.

That is, the positive photoresist composition of the present invention is used in the discharge nozzle type coating method having a process of applying the positive photoresist composition to the entire surface of the substrate by moving the discharge nozzle and the substrate relatively, (A) It is characterized by containing alkali-soluble novolak resin whose polystyrene conversion mass mean molecular weight (Mw) is 6000 or more, (C) naphthoquinone diazide group containing compound, and (D) organic solvent.

In addition, the present invention utilizes the positive type photoresist composition for the discharge nozzle type coating method of the present invention by using the discharge nozzle type coating method of applying the positive type photoresist composition to the entire application surface of the substrate by moving the discharge nozzle and the substrate relatively. It has a process of apply | coating 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 positive photoresist composition to the whole surface of the application | coating surface of a board | substrate by moving a discharge nozzle and a board | substrate relatively, specifically, a some nozzle hole. There exists a method of using the nozzle which has the ejection opening arrange | positioned in this listed shape, the method of using the nozzle which has the ejection opening of a slit shape, etc. Moreover, after apply | coating a photoresist composition to the whole surface of the application | coating surface of a board | substrate in this way, the method of adjusting this film thickness by spinning this 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" means the area | region to which the resist composition should be apply | coated in a board | substrate, and is generally one side whole surface of a board | substrate.

Embodiment of the invention

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

[(A) component]

The alkali-soluble novolak resin (A) used in the present invention can be arbitrarily selected and used among those which can be commonly used as a film forming material in the positive photoresist composition, and as the whole (A) component, a polystyrene reduced mass average molecular weight ( Hereinafter, what is necessary is just to be prepared so that it may become 6000 or more).

When the Mw of the component (A) is less than 6000, it is necessary to increase the resist coating amount in order to prevent streaks. 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 phenols illustrated below and aldehydes illustrated below react with an acid catalyst 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, 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; Polyhydroxyphenols, such as 4,4'- dihydroxy biphenyl, bisphenol A, resorcinol, hydroquinone, a pyrogallol, etc. are mentioned. 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, furyl aldehyde, benzaldehyde, and benzaldehyde. , 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 availability.

As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, oxalic acid, paratoluenesulfonic acid and the like can be used.

In the present invention, the component (A) may be made of one kind of novolac resin, or may be made of two or more kinds of novolac resins. When it consists of 2 or more types of novolak resin, Mw may contain the novolak resin which is not contained in 6000 or more range, and Mw should just be in the range of 6000 or more as the whole (A) component.

[(A1) component, (A2) component]

In the present invention, Mw synthesized using an alkali soluble novolak resin (A) with m-cresol / p-cresol = 20/80 to 40/60 (input ratio) of mixed phenols using formaldehyde as a condensing agent. The novolak resin (A1) having a value of 4000 to 6000 and the mixed phenols of m-cresol / p-cresol = 20/80 to 40/60 (input ratio), Mw synthesized using formaldehyde as a condensing agent is 5000 From -10000, the one containing at least one novolak resin selected from the novolak resin (A2), which is a higher molecular weight than A1, is suitable for the adjustment of a highly sensitive resist composition, and the residual film property of the unexposed part is improved. desirable.

In the above (A1) and (A2), 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 binary nucleus, and is removed during the fractionation operation for the purpose of cutting the low molecular weight body to be 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 Mw of the components (A1) and (A2) is preferably Mw of 4000 to 6000, particularly 4500 to 5500, and the latter (A2) of 5000, in terms of increasing the sensitivity of the resist composition and improving the residual film ratio. It is preferable that they are -10000, especially 5500-6500.

When using 1 or more types of components (novolak resin) chosen from (A1) and (A2) component, the preferable content rate of the sum total of (A1) and (A2) component in (A) component is 10-60 mass. %, More preferably, it is 45-55 mass%. When the content ratio of (A1) and (A2) in (A) component is other than the said range, the effect of high sensitivity and the improvement of a residual film rate is hard to be obtained.

[(A3) component]

Moreover, Mw synthesize | combined using alkali of formaldehyde as a condensing agent with respect to mixed phenols of m-cresol / p-cresol = 50 / 50-70 / 30 (feed ratio) to alkali-soluble novolak resin (A) is 9000 or more It is preferable that the novolak resin (A3) is contained in the point which is excellent in the effect which suppresses generation | occurrence | production of a stripe trace. 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 binary nucleus, and is removed during the fractionation operation for the purpose of cutting the low molecular weight body to be 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 the Mw of the component (A3) is too large, there is a possibility that the sensitivity of the resist composition is lowered or the peelability of the resist pattern in the resist pattern peeling step is adversely affected. If the Mw of the component (A3) is too small, the effect of suppressing the occurrence of streaked traces is small. , 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%. If the content ratio of (A3) in the component (A) is larger than the above range, the sensitivity of the resist composition may decrease, or the peelability of the resist pattern may be adversely affected in the resist pattern peeling step. There is a lack of inhibitory effect.

In the present invention, the component (A) comprises three kinds of the component (A1), the component (A2) and the component (A3), so that the Mw as a whole is within the range of 6000 or more, preferably 15000 or less. It is preferable that it is prepared. In this case, the content ratio of the component (A1), the component (A2) and the component (A3) is preferably in the range of [(A1) + (A2)] / (A3) = 10/90 to 60/40 in mass ratio, The range within 45 / 55-55 / 45 is more preferable.

Moreover, if necessary, (A) component can also contain novolak resins other than (A1), (A2), and (A3). The preferable content rate of the sum total of (A1), (A2), and (A3) in (A) component is 50 mass% or more, More preferably, it is 90 mass% or more. It may be 100 mass%.

[(B) component]

The positive photoresist composition of this invention contains a phenolic hydroxyl group containing compound (B) whose molecular weight (M) is 1000 or less, and a sensitivity improvement effect is acquired. In particular, in the field of manufacturing a liquid crystal display element, since the improvement of throughput is a very big problem and resist consumption tends to increase, it is preferable that it is high sensitivity and low cost in a photoresist composition, and using this (B) component This is preferable because high sensitivity can be achieved at a relatively low cost. 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 the development deviation caused by the difference in the 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, although the phenolic hydroxyl group containing compound of the molecular weight 1000 or less used conventionally for the positive type photoresist composition for liquid crystal display element manufacture can be used suitably, the phenolic hydroxyl group containing compound represented by following General formula (III) Since the sensitivity can be improved effectively, it is more preferable.

[Formula III]

[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 ⁹ to R ¹¹ each independently represent 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, a group which is bonded to R ⁹ to form a cycloalkyl group having 3 to 6 carbon atoms, or a group represented by the following general formula (IV)

[Formula IV]

(In formula, R <^12> and R <^13> respectively independently represents a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a C3-C6 cycloalkyl group; c represents an integer of 1 to 3); a and b represent the integer of 1-3; d represents an integer of 0 to 3; n represents an integer of 0 to 3]

These phenolic hydroxyl group containing compounds may use any 1 type, and may use 2 or more types together.

Among the phenolic hydroxyl group-containing compounds mentioned above, the compound represented by the following general formula (I) is particularly preferable because it is excellent in high sensitivity and high residual film ratio.

[Formula I]

The compounding quantity of (B) 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) is too small in the photoresist composition, the effect of improving the sensitivity and the high residual film ratio is not sufficiently obtained. If the content of the component (B) is too high, residue is likely to occur on the surface of the substrate after development, and the raw material cost is high. It is not desirable because

[(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 products of the phenolic hydroxyl group-containing compound and 1,2-naphthoquinonediazidesulfonic acid compound represented by the following general formula (II) as the component (C) are very inexpensive and have high sensitivity photoresist. It is preferable at the point which a composition can be prepared.

The average esterification rate of this esterification reaction product is 50 to 70%, preferably 55 to 65%, and less than 50% tends to cause post-developmental film reduction and a problem in that the residual film rate becomes low, and 70%. It is not preferable because the storage stability tends to be lowered when it exceeds.

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

[Formula II]

Moreover, in addition to the said photosensitive component, (C) component can use another quinonediazide ester compound, However, It is preferable that these usage amounts are 30 mass% or less, especially 25 mass% or less in (C) component.

As another quinone diazide esterified compound, the phenolic hydroxyl group containing compound and 1,2-naphthoquinone diazide sulfonic-acid compound represented by the said General formula (III), for example, Preferably 1,2-naphthoquinone diazide- Esterification reaction products of 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 parts 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, Preferably, it is desirable to set it in the range of 20-30 mass parts. 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 melt | dissolves (A)-(C) component and various addition components in the organic solvent (D), and uses it in the form of a solution.

As an organic solvent used by this invention, propylene glycol monomethyl ether acetate (PGMEA) is preferable at the point which is excellent in applicability and excellent in the film thickness uniformity of a resist film also 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.

Moreover, 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.

In particular, 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, it is 1.0-2.0 micrometers. After apply | coating a photoresist composition to this, it is preferable to spin this 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% It is preferable to prepare so as to be. As a result, a good coating property is obtained when the photoresist composition is discharged in a band shape from the discharge nozzle and coated on the substrate, and a good fluidity is obtained when the spin is subsequently performed. It is preferable to form the film in a good yield.

[Other Ingredients]

Various additives, such as surfactant and 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.

For example, UV absorbers for antihalation, 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-diethyl Amino azobenzene, glucumin, etc. can be contained suitably.

Moreover, surfactant for preventing streaks, for example, Floraard FC-430, FC431 (product name, manufactured by Sumitomo 3M Co., Ltd.), F-top EF122A, EF122B, EF122C, EF126 (product name, manufactured by Tochem Products Co., Ltd.) Fluorine-type surfactants, such as these, and fluorine-silicone surfactants, such as Megapak R-60 and R-08 (product name, the Dai Nippon Ink Chemical Co., Ltd. product), can be contained suitably.

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

In the case where the adhesion improving agent is contained, when the blending amount is too large, the change over time of the resist composition tends to deteriorate. When the adhesion improving agent is too small, the effect of improving the adhesiveness is not sufficiently obtained, so that 0.1 to 10% by mass of the total solid content is obtained. It is preferable to set it in the range.

The photoresist composition of such a composition is suitable for the coating method of a discharge nozzle system, and when a photoresist composition is discharged in strip shape from a discharge nozzle and apply | coated on a board | substrate, generation | occurrence | production of a striped trace can be prevented. In particular, in the case where the photoresist composition is applied onto 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 about 300 to 500 µm. If it was not formed thick, streaked traces were likely to occur after the spin, but according to the photoresist composition according to the present invention, even if the coating thickness before the spin is formed at about 160 to 250 μm, preferably at about 160 to 200 μm, Stripe traces can be prevented from occurring after spin.

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 coated surface of the substrate by the ejection nozzle type coating method to the required film thickness and the spin is not performed. After apply | coating a photoresist composition to the whole surface of the application | coating surface, it is also suitable for the method of adjusting a film thickness by spinning a board | substrate. In particular, since it is suitable for the latter method and can suppress the stripe trace after spin while suppressing the resist coating amount, it can contribute to reduction of resist consumption amount, yield 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 coating step can be performed by an apparatus provided with a means for relatively moving the discharge nozzle and the substrate. The discharge nozzle may be configured so that the photoresist composition discharged from here may be applied in a band shape on the substrate, and is not particularly limited, but for example, a discharge nozzle having discharge ports arranged in a shape in which a plurality of nozzle holes are arranged; A discharge nozzle having a slit-shaped discharge port can be used. As a coating device having the coating step, TR63000S (product name; manufactured by Tokyo Oka Industries Co., Ltd.) of a coat or spinless method is known.

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

Thus, the process for forming a resist pattern after apply | coating a positive photoresist composition to the whole surface of the application | coating surface of a board | substrate can use a well-known method suitably.

For example, the resist coating is formed by heat-drying (prebaking) the board | substrate to which the photoresist composition was apply | coated at about 100-140 degreeC. Thereafter, the resist film is selectively exposed through a desired mask pattern. The wavelength at the time of exposure can use ghi line | wire (g line | wire, h line | wire, and i line | wire) or i line suitably, respectively, and uses an appropriate light source.

Thereafter, the resist coating after selective exposure is developed using a developing solution composed of an alkaline aqueous solution, for example, an aqueous solution of 1-10 mass% tetramethylammonium hydroxide (TMAH).

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

Then, the resist pattern is obtained by performing a rinse step in which the developer remaining on the surface of the resist pattern is washed with a rinse solution such as pure water after being left to develop for about 50 to 60 seconds.

According to the formation method of such a resist pattern, since the ejection nozzle type coating method is used, a resist film can be formed on a board | substrate without degrading application | coating uniformity and tact time, even if a board | substrate size and apparatus size become large. . In addition, the photoresist composition to be used is adapted to the discharge nozzle method, and the generation of streaked traces on the photoresist film is prevented. In particular, in the case of performing spin after coating, generation of streaked traces can be prevented while suppressing the amount of resist coating, which can contribute to a reduction in manufacturing cost.

EXAMPLE

General physical properties of the positive photoresist composition were obtained as follows.

(1) Evaluation of Stripe Traces:

A predetermined film thickness (160 μm, 180 μm, 200 μm) was applied onto a glass substrate (1100 × 1250 mm 2) on which a Cr film was formed by using a sample (positive photoresist composition) using a coating apparatus (manufactured by Toka Oka Industries, product name TR63000F). Micrometer) and spin to obtain a coating film having a thickness of about 1.5 mu m. The coating device is configured to spin the substrate after applying the photoresist composition to the substrate by the ejection nozzle type coating method.

Subsequently, the temperature of a hotplate is 130 degreeC, the 1st drying for 60 second is performed by the proximity bake with a space of about 1 mm, and then the temperature of a hotplate is 120 degreeC, and 0.5 mm of The 2nd drying for 60 second was performed by the spaced proximity baking, and the resist film with a film thickness of 1.5 micrometers was formed.

, 발생된 것을 ×로 하여 표에 나타냈다.The surface of the obtained resist film was observed under a sodium lamp, and no occurrence of streaked traces was observed.

And generated were shown in the table as x.

(2) Confirmation of Formability of Resist Pattern:

A sample (positive photoresist composition) was applied on a glass substrate (1100 x 1250 mm 2) on which a Cr film was formed with a film thickness of 180 μm using a coating device (manufactured by Toka Oka Industries Co., Ltd., product name TR63000F), and then spinned. It was set as the coating film of about 1.5 micrometers in thickness.

Subsequently, a resist film having a thickness of 1.5 μm was formed in the same manner as the above evaluation of the stripe traces, and then mirror projection through a test chart mask (reticle) in which a mask pattern for reproducing a resist pattern of 3.0 μm line and space was drawn. Exposure was performed using the aligner MPA-600FA (Canon company make: ghi line exposure apparatus). The exposure amount was 40 mJ / cm 2.

Subsequently, the mixture was brought into contact with a 23.degree. C., 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, washed with water for 30 seconds, and spin dried.

(Examples 1-4, Comparative Example 1)

As an Example and a comparative example, the photoresist composition was prepared by the formulation shown in following Table 1, and the evaluation of the stripe trace was performed. The evaluation results are shown in Table 2 below.

In the evaluation of the resist pattern formation ability, in the examples, the resist pattern of 3.0 µm line and space was reproduced in the dimensions on the substrate, but in the comparative example, the resist pattern was changed by the film thickness change caused by the influence of the stripe traces. Dimensional changes were observed in part of.

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

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

(a2): Water-methanol mixed with the 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 = 30/70. The novolak resin of Mw 6300 obtained by fractionating with a solvent.

(a3): Water-methanol mixed with the 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 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): Phenolic hydroxyl group containing compound represented by the said general formula (I) (M = 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 the said General 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 1.1 Molar esterification reaction product.

As the component (D) (organic solvent), 430 parts by mass of the following (d1) was used.

(d1): PGMEA.

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

After dissolving the said (A)-(D) component and other components uniformly, 1000 ppm of Megapak R-60 (product name, the Dainippon Ink & Chemicals Co., Ltd. product) are added as surfactant, and this film | membrane of 0.2 micrometer of pore diameters is added. Filtration was carried out using a filter to prepare a positive photoresist composition.

(A) Component (mixing ratio) (Mw) (B) component (C) component (mixing ratio) (D) component Example 1 a1 / a2 / a3 (40/10/50) (6000) b1 c1 d1 Example 2 a1 / a2 / a3 (20/30/50) (8000) b1 c1 d1 Example 3 a1 / a2 / a3 (10/40/50) (10000) b1 c1 d1 Example 4 a1 / a2 / a3 (20/30/50) (8000) b1 c1 / c2 (1/1) d1 Comparative Example 1 a1                                                  (5000) b1 c1 d1

Evaluation of Stripes Traces 160 μm 180 μm 200 μm Example 1

Example 2

Example 3

Example 4

Comparative Example 1 × × ×

 As explained above, according to this invention, the positive type photoresist composition suitable for the resist coating method by a discharge nozzle type, and the formation method of the resist pattern using the same are obtained.

Claims (13)

A positive photoresist composition used 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) a polystyrene equivalent mass average molecular weight ( A positive photoresist composition for a discharge nozzle type coating method comprising Mw) an alkali-soluble novolak resin having a 6000 or more, a (C) naphthoquinone diazide group-containing compound, and (D) an organic solvent. Mw of said (A) alkali-soluble novolak resin synthesize | combined using formaldehyde as a condensing agent with respect to mixed phenols of m-cresol / p-cresol = 20 / 80-40 / 60 (feed ratio) 4000-6000 The mixed phenols of the phosphorus novolak resin (A1) component and m-cresol / p-cresol = 20/80 to 40/60 (feed ratio) were synthesized using formaldehyde as a condensing agent as 5000 to 10,000. Condensed formaldehyde with respect to a mixed phenol of at least one selected from novolak resin (A2) components which are higher molecular weights than the above-mentioned A1, and m-cresol / p-cresol = 50/50 to 70/30 (input ratio). The mass ratio of content of 1 or more types chosen from said (A1) component and (A2) component, and content of said (A3) component is contained, and Mw synthesize | combined using as a agent contains 9000 or more novolak resin (A3) component Positivity for a discharge nozzle-type coating method whose value of [(A1) + (A2)] / (A3) which are shown is 10/90-60/40 Photoresist composition. 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 (M) of 1000 or less. delete delete delete delete 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 general formula (I). [Formula I]

The ejection according to claim 1, wherein the component (C) contains an esterification reaction product of a phenolic hydroxyl group-containing compound represented by the following general formula (II) with a 1,2-naphthoquinone diazide sulfonic acid compound. Positive photoresist composition for the nozzle coating method. [Formula II]

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 the discharge nozzle type coating method according to claim 1, wherein the discharge nozzle coating method has a step of applying the positive photoresist composition to the entire coated surface of the substrate and then spinning the substrate. Resist composition. The positive type photoresist of any one of Claims 1, 2, and 7-11 which is a method of apply | coating a positive photoresist composition to the whole surface of the application | coating surface of a board | substrate by moving a discharge nozzle and a board | substrate relatively. It has a process of apply | coating a resist composition on a board | substrate, The formation method of the resist pattern characterized by the above-mentioned. 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.