JP4611690B2 - Method for forming resist pattern, method for forming fine pattern using the same, and method for manufacturing liquid crystal display element - Google Patents

Description

The present invention is a method for forming a resist pattern relates to the production method of forming method and a liquid crystal display device of a fine pattern using the same.

For example, a photolithography process using a photoresist film is used to manufacture a TFT (Thin Film Transistor) array substrate of a liquid crystal display element.
2 to 15 show an example of a process for manufacturing an α-Si (amorphous silica) type TFT array substrate having the structure shown in FIG. In this example, first, as shown in FIG. 2, a gate electrode layer 2 ′ is formed on the glass substrate 1.
Next, a photoresist film is formed on the gate electrode layer 2 ′, and the photoresist film is patterned by photolithography including a step of selectively exposing through a mask to form a resist pattern R1 as shown in FIG. (First photolithography process).
Then, after etching the gate electrode layer 2 ′ using the obtained resist pattern R1 as a mask, the resist pattern R1 is removed to form the gate electrode 2 as shown in FIG.

Subsequently, as shown in FIG. 5, the first insulating film 3 is formed on the glass substrate 1 on which the gate electrode 2 is formed, and further the first α-Si layer 4 ′ and the etching stopper film 5 are formed thereon. 'In order.
A photoresist film is formed on the etching stopper film 5 ′, and the photoresist film is patterned by photolithography including a step of selectively exposing through a mask to form a resist pattern R2 as shown in FIG. Photolithography process).
Then, after etching the etching stopper film 5 ′ and the first α-Si layer 4 ′ using the obtained resist pattern R2 as a mask, the resist pattern R2 is removed, whereby the patterning as shown in FIG. A laminated body of the 1 α-Si layer 4 and the etching stopper film 5 is formed.
A second α-Si layer 6 ′ and a source / drain electrode forming metal film 7 ′ are sequentially formed thereon, as shown in FIG.

Then, a photoresist film is formed on the metal film 7 ′, and the photoresist film is patterned by photolithography including a step of selectively exposing through a mask to form a resist pattern R3 as shown in FIG. Third photolithography process).
Thereafter, using the obtained resist pattern R3 as a mask, the metal film 7 ′ and the second α-Si layer 6 ′ are etched, and then the resist pattern R3 is removed to obtain an etching stopper film as shown in FIG. A patterned second α-Si layer 6 and source and drain electrodes 7 are formed on the substrate 5.

Subsequently, as shown in FIG. 11, a second insulating film 8 ′ is formed on the glass substrate 1.
Then, a photoresist film is formed on the second insulating film 8 ′, and the photoresist film is patterned by photolithography including a step of selectively exposing through a mask to form a resist pattern R4 as shown in FIG. Form (fourth photolithography process).
Thereafter, the second insulating film 8 ′ is etched using the obtained resist pattern R4 as a mask, and then the resist pattern R4 is removed, thereby forming a first patterned pattern having a contact hole as shown in FIG. Two insulating films 8 are formed.

Subsequently, as shown in FIG. 14, a transparent conductive film 9 ′ is formed on the glass substrate 1.
Then, a photoresist film is formed on the transparent conductive film 9 ′, and the photoresist film is patterned by photolithography including a step of selectively exposing through a mask to form a resist pattern R5 as shown in FIG. (Fifth photolithography process).
Thereafter, the transparent conductive film 9 ′ is etched using the obtained resist pattern R5 as a mask, and then the resist pattern R5 is removed to form a patterned transparent conductive film 9 as shown in FIG. A substrate is obtained.

In the method of manufacturing a TFT array substrate through such steps, a total of five photolithography steps (first to fifth photolithography steps) for performing selective exposure using a photomask have been performed.
Incidentally, in recent years, there has been a strong demand for cost reduction of liquid crystal display elements. For this reason, simplification of the manufacturing process, suppression of resist consumption, and the like are required.
Therefore, in order to meet such a demand, by using a step-shaped resist pattern having different thicknesses depending on regions, a process that conventionally used two photolithography processes is performed in one photolithography process. A method has been proposed. In this method, after performing etching using the stepped resist pattern as a mask, by utilizing the difference in thickness, the planar shape of the stepped resist pattern is deformed without depending on the photolithography process. Etching is performed again using the mask.

Patent Documents 1 to 4 describe a technique for reducing the number of photolithography processes, and Patent Documents 5 to 6 describe performing an ultraviolet irradiation process on a resist pattern.
JP 2004-171002 A JP 2002-334830 A JP 2000-133636 A JP 2000-131719 A Japanese Patent Laid-Open No. 9-15851 Japanese Patent No. 2552648

According to the above method, since the number of photolithography processes can be reduced theoretically, the consumption of the photoresist can be suppressed and the process can be simplified. It is expected to be effective for manufacturing.
However, even if an attempt is made to form such a stepped resist pattern with a resist material that has been suitable for manufacturing conventional liquid crystal display elements, the etching resistance and heat resistance are insufficient, and it is difficult to realize such a method. .

Specifically, as described above, since the stepped resist pattern is used as an etching mask before and after the deformation, it needs to have high etching resistance, but has such high etching resistance. It is difficult to form a stepped resist pattern.
In addition, resist patterns used in liquid crystal display element manufacturing may be post-baked to increase heat resistance so that they can withstand etching processes and implantation processes. Resist materials that have been considered suitable are inexpensive and highly sensitive, but tend to be inferior in heat resistance. As a result, post-baking treatment causes the stepped resist pattern to flow, maintaining the shape with different thicknesses. Difficult to do.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for forming a resist pattern that is excellent in etching resistance and heat resistance and that can form a stepped resist pattern.
It is another object of the present invention to provide a fine pattern forming method using the resist pattern forming method of the present invention, and a liquid crystal display device manufacturing method using the same.
Another object of the present invention is to provide a positive resist composition used in the resist pattern forming method and fine pattern forming method of the present invention.

In order to achieve the above object, a resist pattern forming method of the present invention includes (A) a step of forming a photoresist film on a substrate, and (B) a photolithography step including selective exposure through a halftone mask. , The step of patterning the photoresist film into a stepped resist pattern having a thick portion and a thin portion, and (D) a step of performing a post-bake treatment, the steps (B) and (D) (C) a resist pattern forming method that does not include a step of performing UV curing, and (a) an alkali-soluble novolak resin having a polystyrene-reduced mass average molecular weight (Mw) of more than 8000 by gel permeation chromatography (B) a naphthoquinonediazide group-containing compound, and (d) a positive-type photoresist containing an organic solvent Using preparative composition to form the photoresist film, as the substrate, a gate electrode on a glass substrate, a first insulating film, a first amorphous silica film, an etching stopper film, the second amorphous silica film, and a source The metal film for forming a drain electrode is characterized in that a metal film having a multilayer structure laminated in order from the glass substrate side is used .

The fine pattern forming method of the present invention is the resist pattern forming method of the present invention. After forming a stepped resist pattern having a thick portion and a thin portion, (E) the substrate using the stepped resist pattern as a mask (F) An ashing process (ashing process) is performed on the stepped resist pattern to remove the thin part, and (G) the thick part is removed after the thin part is removed. Etching is performed on the substrate using a portion as a mask, and then (H) a step of removing the thick portion of the stepped resist pattern.
According to another aspect of the method for forming a fine pattern of the present invention, after forming a stepped resist pattern having a thick portion and a thin portion, (E) the substrate is etched using the stepped resist pattern as a mask. (F) An ashing process (ashing process) is performed on the stepped resist pattern to remove the thin part. (G) After removing the thin part, the thick part is used as a mask. A method for forming a fine pattern, which includes a step of etching the substrate, and then (H) removing a thick portion of the stepped resist pattern, wherein the stepped resist pattern is formed by (A) the substrate. A step of forming a photoresist film thereon, (B) a photolithographic process including selective exposure through a halftone mask, and then forming the photoresist film into a stepped shape having a thick part and a thin part. And (D) a step of performing post-baking treatment, and (C) a step of performing UV curing treatment between the step (B) and the step (D). The stepwise resist pattern is formed by the following steps: (a) an alkali-soluble novolak resin having a polystyrene-reduced mass average molecular weight (Mw) of more than 8000 by gel permeation chromatography, (b) naphtho The photoresist film is formed using a positive photoresist composition containing a quinonediazide group-containing compound and (d) an organic solvent.

Alternatively, the fine pattern forming method of the present invention is a resist pattern forming method of the present invention using the substrate having the multilayer structure, and after forming a stepped resist pattern having a thick part and a thin part, (E ′ After etching the source / drain electrode forming metal film, the second amorphous silica film, the etching stopper film, and the first amorphous silica film using the stepped resist pattern as a mask, (F) the step Ashing (ashing treatment) is performed on the resist pattern to remove the thin portion, and (G ′) the thin portion is removed, and then the metal film for forming the source / drain electrodes is formed using the thick portion as a mask. And etching the second amorphous silica film to expose the etching stopper film layer, and then (H) the stepped resister. And wherein further comprising the step of removing the thick portion of the bets pattern.

The method for producing a liquid crystal display element of the present invention is a method for producing a liquid crystal display element having a step of forming a pixel pattern on a glass substrate, and a part of the pixel pattern is formed by the method for forming a fine pattern of the present invention. It is characterized by forming.
Alternatively, in the method of manufacturing a liquid crystal display element of the present invention, after forming a fine pattern by the fine pattern forming method of the present invention using the substrate having the multilayer structure, (I) a second insulating film on the fine pattern (J) a step of patterning the second insulating film by photolithography, (K) a step of forming a transparent conductive film on the patterned second insulating film, and (L) photolithography of the transparent conductive film. And a patterning step.

  According to the method for forming a resist pattern of the present invention, among the positive resist compositions using an alkali-soluble novolak resin as a resin component and a naphthoquinonediazide group-containing compound as a photosensitive component, in particular, the Mw of the alkali-soluble novolak resin. By using a positive resist composition having the above specific range, it is possible to form a stepped resist pattern having good heat resistance and etching resistance and excellent shape stability.

According to the fine pattern forming method of the present invention, the etching resistance of the stepped resist pattern is excellent. Therefore, after etching the substrate using the stepped resist pattern as a mask, the thin portion of the stepped resist pattern is ashed. The substrate can be etched using again the mask removed by the treatment. Therefore, the number of photolithography processes for patterning a photoresist film using a photomask can be reduced.
As a result, the consumption of photoresist can be suppressed, the cost of a relatively expensive photomask can be reduced, and the process can be simplified.

  The positive resist composition of the present invention uses an alkali-soluble novolak resin as a resin component, and among the positive resist compositions using a naphthoquinonediazide group-containing compound as a photosensitive component, in particular, the Mw of the alkali-soluble novolak resin is the above. Therefore, a resist pattern formed by patterning a photoresist film made of this composition has good heat resistance and etching resistance and is excellent in shape stability. Accordingly, such a positive resist composition is suitable as a photoresist film material for forming a stepped resist pattern in the resist pattern forming method and the fine pattern forming method of the present invention.

  According to the method for manufacturing a liquid crystal display element of the present invention, the number of photolithography processes in the process of forming a pixel pattern on a glass substrate can be reduced, thereby reducing the consumption of photoresist and reducing the photomask used. Can be realized. Further, since the manufacturing process can be simplified, it is effective for manufacturing an inexpensive liquid crystal display element.

<Positive photoresist composition>
[(A) component]
The alkali-soluble novolak resin (a) of the positive resist composition according to the present invention can be arbitrarily selected from those normally used as a film-forming substance in the positive photoresist composition, and (a) As a whole component, the polystyrene-reduced mass average molecular weight (sometimes only described as Mw in this specification) by gel permeation chromatography (sometimes abbreviated as GPC in this specification) exceeds 8,000. What is prepared should just be.
(A) By making Mw of component over 8000, it has high heat resistance that does not cause flow phenomenon during heating in post-baking treatment, etc., and has good etching resistance, especially dry etching resistance. It is possible to realize a stepped resist pattern excellent in the above. As the value of Mw is larger, higher heat resistance and etching resistance can be achieved. A more preferable range of Mw of the component (a) is 10,000 or more. However, since the resist sensitivity tends to be inferior when the Mw of the component (a) is too large, the upper limit value of the Mw of the component (a) is preferably 80000 or less, more preferably 50000 or less.

Specific examples of the alkali-soluble novolak resin (a) include novolak resins obtained by reacting phenols exemplified below with aldehydes exemplified below under 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, p-cresol, and 2,3,5-trimethylphenol 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 it is easily available. In particular, in order to improve heat resistance, it is preferable to use a combination of hydroxybenzaldehydes and formaldehyde.
As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, oxalic acid, p-toluenesulfonic acid and the like can be used.

  Further, by suppressing the dinuclear content in the component (a) to a low level, the amount of degassing when heat treatment such as post-baking is performed is reduced, and the shrink phenomenon of the stepped resist pattern, macroporous It is preferable because generation of cracks and the like can be prevented and contamination in the processing chamber due to degassing from the stepped resist pattern can be suppressed.

Here, the binuclear body in the present invention is a condensate molecule having two phenol nuclei, and the binuclear body content is the abundance ratio on the chromatogram at a detection wavelength of 280 nm by GPC. In this specification, the content measured using the following GPC system is specifically used for the content of the binuclear body.
Device name: SYSTEM 11 (product name, Showa Denko)
Precolumn: KF-G (product name, manufactured by Shodex)
Column: KF-802 (product name, manufactured by Shodex)
Detector: UV41 (product name, manufactured by Shodex), measured at 280 nm.
Solvent etc .: Tetrahydrofuran was allowed to flow at a flow rate of 1.0 ml / min and measured at 35 ° C.

The binuclear content in the component (a) is preferably 4.0% or less. The amount of degassing during heating can be further reduced as the dinuclear content in component (a) is smaller, but the production cost increases as the content of dinuclear is smaller, so the content of dinuclear in component (a) The lower limit of the amount is preferably about 0.1%. A more preferable range of the binuclear content in the component (a) is about 1.0 to 3.0%.
(A) Mw and binuclear content of component are obtained by synthesizing a condensate of phenols and aldehydes by a synthesis reaction of a normal novolak resin, and then cutting a low molecular region by a known fractionation operation. Can be adjusted.
For the treatment such as fractionation, for example, the novolak resin obtained by the condensation reaction is dissolved in a good solvent, for example, alcohol such as methanol or ethanol, ketone such as acetone or methyl ethyl ketone, ethylene glycol monoethyl ether acetate, tetrahydrofuran or the like, It can be performed by a method such as pouring into water for precipitation.
Alternatively, the binuclear content can also be reduced by performing, for example, steam distillation during the synthesis reaction (condensation reaction) of the novolak resin (Japanese Patent Laid-Open No. 2000-13185).

The component (a) may be composed of one type of novolac resin or may be composed of two or more types of novolac resins. When composed of two or more types of novolac resins, it may contain a Mn of more than 8000, preferably a novolak resin not included in the range of the binuclear content of 4% or less. The dinuclear content should be 4% or less. Therefore, the Mw and binuclear content of the component (a) can also be adjusted by appropriately mixing and using two or more novolak resins having different Mw and binuclear content.
[Component (b)]
(B) A naphthoquinonediazide group-containing compound is a photosensitive component. As this (b) component, what was conventionally used as a photosensitive component of the positive photoresist composition for liquid crystal display element manufacture can be used, for example.
For example, as the component (b), an esterification reaction product (b1) of a phenolic hydroxyl group-containing compound represented by the following formula (I) and a 1,2-naphthoquinonediazide sulfonic acid compound and / or the following formula (II) The esterification reaction product (b2) of the represented phenolic hydroxyl group-containing compound and 1,2-naphthoquinonediazide sulfonic acid compound can be preferably used. The 1,2-naphthoquinonediazide sulfonic acid compound is preferably a 1,2-naphthoquinonediazide-5-sulfonyl compound.

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

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

The average esterification rate of the component (b1) 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 that the remaining film rate is low. If it exceeds 70%, the storage stability tends to decrease, such being undesirable.
The average esterification rate of the component (b2) is 40 to 60%, preferably 45 to 55%. If it is less than 40%, film loss after development tends to occur and the remaining film rate tends to be low. If it exceeds 60%, the sensitivity tends to deteriorate significantly.
As the component (b2), an esterification reaction product (b3) of a phenolic hydroxyl group-containing compound represented by the following formula (IV) and a 1,2-naphthoquinonediazide sulfonic acid compound has a particularly high resolution resist pattern. It is preferable because of its excellent forming ability.

  As the component (b), 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 (b) Preferably there is.

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

As the component (b), the component (b1) is particularly preferable because it is very inexpensive and can prepare a highly sensitive photoresist composition and has excellent heat resistance.
Further, as the component (b), a preferable component can be selected according to the exposure wavelength used in the development process. For example, in the step of performing selective exposure, when performing ghi line (g line, h line, and i line) exposure, (b1) can be preferably used, and when performing i line exposure, component (b2) is used. It is preferable to use or use (b1) and (b2) in combination.
In particular, when i-line exposure is performed, when (b1) and (b2) are used in combination, the blending ratio of (b1) to (b2) is preferably 50 parts by mass or less. If the blending amount of (b1) is too large, the resolution and sensitivity may be greatly lowered.

[Component (c)]
The positive photoresist composition according to the present invention preferably contains a phenolic hydroxyl group-containing compound (c) 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 since the resist consumption is large, it is desirable that a photoresist composition is highly sensitive and inexpensive. Use of the component c) is preferable because high sensitivity can be achieved at a relatively low cost. In addition, when the component (c) is contained, a surface hardly-solubilized layer is strongly formed in the resist pattern, so that the amount of unremoved resist film 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 (c) exceeds 1000, the effect of improving the sensitivity is not obtained so much.
As the component (c), a phenolic hydroxyl group-containing compound having a molecular weight of 1000 or less, which is conventionally used in positive photoresist compositions for producing liquid crystal display elements, can be used as appropriate, and is represented by the following general formula (II). The phenolic hydroxyl group-containing compound is more preferable because it can effectively improve sensitivity and has good heat resistance.

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

Wherein R ¹² and R ¹³ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. C represents an integer of 1 to 3); a and b represent an integer of 1 to 3; d represents an integer of 0 to 3; and n represents an integer of 0 to 3]
These may use any 1 type and may use 2 or more types together.

  Among the phenol compounds, a compound represented by the following formula (V) (1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene), and Bis (2,3,5-trimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane is particularly preferred because of its high sensitivity and high residual film ratio, and the compound represented by the formula (V) is particularly high. It is preferable in terms of excellent sensitivity.

(C) 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% is preferable. If the content of the component (c) in the photoresist composition is too low, the effect of improving the sensitivity and the remaining film ratio cannot be sufficiently obtained, and if it is too much, a residue is easily generated on the substrate surface after development. Also, the raw material cost is increased, which is not preferable.

[Component (d)]
In the photoresist composition according to the present invention, the components (a) and (b), preferably the components (a) to (c), and various additive components are dissolved in the organic solvent (d) and used in the form of a solution. Is preferred.
As the organic solvent (d), propylene glycol monomethyl ether acetate (PGMEA) is preferable because it is excellent in coatability and the film thickness uniformity of the resist film on a large glass substrate.
PGMEA is most preferably used as a single solvent, but solvents other than PGMEA can also be used, and examples thereof include ethyl lactate, γ-butyrolactone, propylene glycol monobutyl ether and the like.
In the case of using ethyl lactate, it is desirable to blend in an amount of 0.1 to 10 times, preferably 1 to 5 times the mass ratio of PGMEA.
Moreover, when using (gamma) -butyrolactone, it is desirable to mix | blend in 0.01-1 times amount by mass ratio with respect to PGMEA, Preferably it is 0.05-0.5 times amount.

  In the present invention, when forming a resist film for forming a stepped resist pattern, the thickness of the photoresist film is set to 1.0 to 3.0 μm, particularly 1.5 to 2.5 μm. For this purpose, the total amount of the components (a) to (c) in the photoresist composition is 30% by mass or less based on the total mass of the composition. In order to obtain good coating properties, it is preferable to adjust to 20 to 28% by mass.

[Other ingredients]
Various additives such as a surfactant and a storage stabilizer can be used in the photoresist composition according to 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, etc., and an interface for preventing striations Activating agents, for example, fluorosurfactants such as Florard FC-430, FC431 (trade name, manufactured by Sumitomo 3M Co., Ltd.), Ftop EF122A, EF122B, EF122C, EF126 (trade name, manufactured by Tochem Products Co., Ltd.) , Mega Fuck R-60 (trade name, Dainippon Ink Fluorine Industry Co., Ltd.) - silicon-based surfactant, BYK-310 (trade name, may be appropriately contained by BYK Co., Ltd.) and the like.

Hereinafter, an embodiment in which a resist pattern forming method and a fine pattern forming method using the resist pattern forming method of the present invention are applied to the manufacture of a liquid crystal display element will be described with reference to FIG.
First, a substrate is prepared. The substrate in the present invention is not particularly limited, but it is preferable to use a substrate in which two or more layers to be etched are stacked on the substrate because the effects of the present invention can be obtained effectively.
When manufacturing a liquid crystal display element, as shown in FIG. 1A, for example, as a substrate 10, a gate electrode 2, a first insulating film 3, a first amorphous silica film 4 ′, A film having a multilayer structure in which an etching stopper film 5 ′, a second amorphous silica film 6 ′, and a source / drain electrode forming metal film 7 ′ are sequentially laminated from the glass substrate 1 side is used. The patterning of the gate electrode 2 can be performed by the procedure (including the first photolithography process) shown in FIGS.
The size of the glass substrate is not particularly limited, but can be a large substrate of 500 × 600 mm ² or more, particularly 550 × 650 mm ² or more.

The gate electrode 2 is formed using a conductive material such as a metal such as aluminum (Al), chromium (Cr), titanium (Ti), or molybdenum (Mo).
The first insulating film 3 is made of, for example, SiN _X.
The etching stopper film 5 ′ is made of, for example, SiN _X.
The source / drain electrode forming metal film 7 ′ is composed of, for example, a laminated film in which titanium (Ti), aluminum (Al), and titanium (Ti) are laminated in this order.

(A) First, a photoresist film R ′ is formed on the substrate 10. Specifically, a photoresist composition R ′ is formed by applying a photoresist composition on the substrate 10 and heating and drying (prebaking) at about 100 to 140 ° C.
The thickness of the photoresist film R ′ is preferably about 1.0 to 3.0 μm. Setting the thickness of the photoresist film R ′ within this range is preferable in terms of both resist sensitivity and manufacturing stability.
(B) Next, through a photolithography process, as shown in FIG. 1B, the photoresist film R ′ is patterned into a pattern having a thick part r1 and a thin part r2. Specifically, for example, the photoresist film R ′ is selectively exposed through a mask (reticle) having a set transmittance such as a halftone mask, followed by development and water washing, thereby increasing the thickness of the region. The stepped resist pattern R having the thick part r1 and the thin part r2 is formed. (Second photolithography process)
The difference in thickness between the thick part r1 and the thin part r2 in the stepped resist pattern R is to remove only the thin part r2 by a subsequent ashing process and leave the thick part r1 at a suitable thickness. The range is preferably about 0.5 to 1.5 μm, and more preferably about 0.7 to 1.3 μm.

(C) After patterning, UV (ultraviolet) curing treatment is preferably performed.
In the present invention, UV curing treatment is not essential, but by performing this, the etching resistance and heat resistance of the stepped resist pattern R can be further improved.
UV curing can be performed using a known method. For example, the entire surface of the stepped resist pattern R is irradiated with ultraviolet rays using an ultraviolet irradiation device such as “Product Name: UMA-802-HC552” manufactured by USHIO.
In order to obtain a stepped resist pattern R having excellent etching resistance and good heat resistance without changing the shape of the resist pattern by UV curing, in particular, the UV irradiation condition is a wavelength ranging from the Deep UV region to the visible light region. It is preferable to irradiate ultraviolet rays having a wavelength of about 200 to 500 nm at an irradiation amount of about 1000 to 50000 mJ / cm ² . A more preferable irradiation amount is about 2000 to 20000 mJ / cm ² . The amount of irradiation can be controlled by the intensity of the irradiated ultraviolet rays and the irradiation time.
In UV curing (irradiation), it is desirable to control the temperature increase due to rapid irradiation or irradiation so that wrinkles are not generated in the irradiated portion.

(D) Moreover, it is preferable to perform a post-bake treatment on the stepped resist pattern R. When performing the UV curing process, post-baking is performed after the UV curing process.
When UV curing is performed, post-baking is not essential, but post-baking further improves the heat resistance and etching resistance of the stepped resist pattern R, particularly dry etching. Further, since the adhesion between the stepped resist pattern R and the substrate 10 is improved by the post-bake treatment, it is effective in obtaining high resistance to the wet etching treatment.
In the present invention, the positive resist composition itself used for forming the photoresist film has high etching resistance. Therefore, even if the temperature condition in the post-baking process is set low, the etching resistance by post-baking is effectively reduced. Can be improved.
For example, the heating conditions in the post-bake treatment can be preferably set to a temperature condition of 100 to 150 ° C. and a heating time of about 1 to 5 minutes. More preferable heating conditions are 110 to 130 ° C. and about 1 to 2 minutes. In particular, in order to surely prevent a change in the shape of the stepped resist pattern R, it is preferable to perform under a temperature condition of 120 ° C. or less.
Since the positive resist composition itself used for forming the photoresist film has high heat resistance, deformation of the stepped resist pattern R in the post-baking process can be suppressed from this point. Further, when the post-baking process is performed after the UV curing process, the heat resistance of the stepped resist pattern R is further improved by the UV curing process, so that pattern deformation due to the post-baking process can be suppressed more reliably. .

(E) Thereafter, using the stepped resist pattern R as a mask, the metal film 7 ′ of the substrate 10 is etched as shown in FIG. Etching of the metal film 7 ′ can be performed by a known method. In general, wet etching is used, but dry etching may be used.
Subsequently, using the same stepped resist pattern R as a mask, as shown in FIG. 1D, the second amorphous silica film 6 ′ exposed by the etching of the metal film 7 ′ and the etching stopper film 5 therebelow are exposed. 'And the first amorphous silica film 4' are etched. Etching of these layers can be performed by a known method. Generally, a dry etching process is used.
Here, although there are a physical method and a chemical method in the dry etching process, any of them can be used in the present invention, and can be appropriately selected according to the material to be etched.

(F) Thereafter, the stepped resist pattern R is subjected to ashing to remove the thin portion r2 as shown in FIG. The ashing process can be performed by a known method. When the stepped resist pattern R is subjected to the ashing process, the thick part r1 and the thin part r2 are simultaneously reduced in thickness, eventually the thin part r2 is completely removed, and the underlying metal film 7 ′ is exposed, The thick part r1 remains. By stopping the ashing process in this state, only the thin portion r2 can be removed. If the remaining thick part r1 is too thin, the function as an etching mask becomes insufficient. Therefore, the thickness of the remaining thick part r1 is preferably 0.5 μm or more.

(G) Subsequently, as shown in FIG. 1 (f), the metal film 7 ′ exposed by the removal of the thin portion r2 is etched using the remaining thick portion r1 as a mask, so that the source electrode and A drain electrode 7 is formed.
Subsequently, as shown in FIG. 1G, the second amorphous silica film 6 ′ exposed by the previous etching process of the metal film 7 ′ is etched using the remaining thick part r1 as a mask, A patterned second amorphous silica film 6 is formed.
(H) After that, the thick part r1 is removed. The removal method of the thick part r1 can be performed by a known method such as an ashing process.
Through the steps so far, a fine pattern having the same structure as that shown in FIG. 10 is obtained.

Thereafter, the TFT array substrate can be manufactured by the same process as that shown in FIGS. That is,
(I) As shown in FIG. 11, a second insulating film 8 ′ is formed on the fine pattern obtained in the previous step. The second insulating film 8 ′ is made of, for example, SiN _X.
(J) A photoresist film is formed on the second insulating film 8 ′, and the photoresist film is patterned by photolithography including a step of selectively exposing through a mask to form a resist pattern R4 as shown in FIG. Form (third photolithography process). The second insulating film 8 ′ is etched using the obtained resist pattern R4 as a mask, and then the resist pattern R4 is removed, whereby the second pattern patterned into a shape having a contact hole as shown in FIG. An insulating film 8 is obtained.
(K) As shown in FIG. 14, a transparent conductive film 9 ′ is formed on the patterned second insulating film 8. The transparent conductive film 9 ′ is made of, for example, ITO (Indium Tin Oxide).
(L) A photoresist film is formed on the transparent conductive film 9 ′, and the photoresist film is patterned by photolithography including a step of selectively exposing through a mask to form a resist pattern R5 as shown in FIG. (Fourth photolithography process).
Thereafter, the transparent conductive film 9 ′ is etched using the obtained resist pattern R5 as a mask, and then the resist pattern R5 is removed to form a patterned transparent conductive film 9 as shown in FIG. A substrate is obtained.
A liquid crystal display element is obtained by assembling by a known method so that the liquid crystal is sandwiched between the TFT array substrate thus obtained and the counter substrate.

According to the present embodiment, a stepped resist pattern R having high etching resistance can be formed. Therefore, using the stepped resist pattern R as a mask, the metal film 7 ′ of the base 10 and the second amorphous silica film 6 are formed. After etching the etching stopper film 5 ′ and the first amorphous silica film 4 ′, the metal film 7 ′ and the second amorphous silica film 6 ′ are formed using the thick portion r1 of the stepped resist pattern R as a mask. It can be etched.
Accordingly, the number of photolithography processes in the TFT array substrate manufacturing process can be reduced. For example, in the conventional method shown in FIGS. 2 to 15, five photolithography steps are required to manufacture the TFT array substrate (first to fifth photolithography steps). In this embodiment, A TFT array substrate having the same structure can be manufactured by four photolithography processes (first to fourth photolithography processes). As a result, consumption of the photoresist can be suppressed and the process can be simplified, so that the manufacturing cost of the TFT array substrate can be reduced.
Further, since the stepped resist pattern R formed in the present embodiment has good heat resistance, deformation in the post-baking process is prevented.
Furthermore, by performing UV curing treatment and / or post-baking treatment, the heat resistance and etching resistance of the stepped resist pattern R can be further improved. If both the UV curing process and the post-baking process are performed, the heat resistance and etching resistance of the stepped resist pattern R can be further improved.

In this embodiment, the stepped resist pattern has a concave cross section. However, the stepped resist pattern may have a different thickness depending on the region, and may have a thick part and a thin part. The fine pattern formed by is designed as appropriate according to the shape. For example, the cross-sectional convex shape in which the thin part is provided in the outer side of the thick part may be sufficient, and the cross-sectional mountain shape may be sufficient.
In the present embodiment, the present invention is applied to a process for manufacturing an α-Si (amorphous silica) TFT array substrate having the structure shown in FIG. 16, but the present invention is not limited to this example. The present invention is applicable to the manufacture of a liquid crystal panel substrate having a pixel pattern provided with various drive elements, and is particularly suitable for the manufacture of a TFT array substrate having a pixel pattern provided with TFT elements having various structures. By forming a part of the pixel pattern by using the fine pattern forming method of the present invention, the same effect as in the present embodiment can be obtained.

  In the following Examples and Comparative Examples, stepped resist patterns were formed by the following resist pattern forming methods 1 to 4, and the heat resistance, dry etching resistance, and wet etching resistance were evaluated by the following methods.

(Resist pattern formation method 1: No UV cure, post-bake at 120 ° C)
The prepared positive photoresist composition is liquid-filled with a predetermined film thickness (50 μm) using a resist coating apparatus [TR-36000 (manufactured by Tokyo Ohka Kogyo Co., Ltd.)] by a central dropping & spin coating method, By rotating at 1000 rpm for 10 seconds, a resist layer was formed on a glass substrate (360 mm × 460 mm) on which a Ti film was formed.
Next, the temperature of the hot plate is set to 130 ° C., the first drying is performed for 60 seconds by proximity baking with an interval of about 1 mm, and then the temperature of the hot plate is set to 120 ° C. with an interval of 0.5 mm. A second drying for 60 seconds was performed by proximity baking to form a photoresist film having a thickness of 2.0 μm.
The photoresist film is selectively exposed through a mask, developed, and washed to have a concave cross section as shown in FIG. 1, with a thickness of 2.0 μm and a thickness of 1. Patterning was performed in the form of a stepped resist pattern having a width of 0 μm, an overall width of 15 μm, and a thin portion having a width of 5 μm.
Thereafter, a post-baking process at 120 ° C. for 180 seconds was performed to obtain a stepped resist pattern.

(Resist pattern formation method 2: No UV cure, post-bake 130 ° C)
A stepped resist pattern was formed in the same manner as in the resist pattern forming method 1 except that the post-baking temperature was changed to 130 ° C.
(Resist pattern formation method 3: with UV cure, without post-bake)
In the resist pattern forming method 1, a post-baking process is not performed after patterning, and a stepped resist pattern is formed in the same manner except that a UV curing (irradiation) process with a wavelength of 200 to 500 nm and an irradiation amount of 3000 mJ / cm ² is performed instead. Formed.
(Resist pattern formation method 4: with UV cure, post-baking at 120 ° C.)
In the resist pattern forming method 1, the patterning was performed in the same manner except that a UV curing (irradiation) treatment with a wavelength of 200 to 500 nm and an irradiation amount of 3000 mJ / cm ² was performed after patterning, and a post-baking treatment at 120 ° C. for 180 seconds. A resist pattern was formed.

(1) Heat resistance evaluation:
The resist patterns obtained in the examples and comparative examples were subjected to a heat treatment at 130 ° C. for 300 seconds, and the resist pattern shape that was not deformed was indicated as “◯” and the deformed pattern as “X”.
(2) Dry etching resistance evaluation:
A dry etching apparatus “TCE-7612X” (apparatus name; manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used for the resist patterns obtained in the examples and comparative examples, and CF ₄ , CF ₃ , and He were used as etching gases, respectively. Used at milliliters / min, 40 milliliters / min, 160 milliliters / min, under a reduced pressure atmosphere of 300 mTorr- ¹ , 700 W-400 kHz, stage temperature: 20 ° C., target temperature: 25 ° C. The case where the resist pattern shape was not deformed before and after was indicated as ◯, and the case where the resist pattern was slightly deformed was indicated as Δ.
(3) Wet etching resistance evaluation:
Wet etching solution [hydrofluoric acid (HF) / ammonium fluoride (NH ₄ F)] set to 20 ° C. with respect to the resist patterns obtained in Examples and Comparative Examples. = 20% by weight aqueous solution containing 1/6 (mass ratio) mixture] Wet etching treatment was performed by immersing in 10 minutes, and the resist pattern after the treatment was not peeled off from the base substrate. The slightly peeled product was indicated by Δ, and the peeled product was indicated by ×.

Example 1
A positive photoresist composition was prepared.
(A) Component: cresol novolak resin [m-cresol / p-cresol = 4/6 (molar ratio) mixed phenols and formaldehyde obtained by a condensation reaction by a conventional method, mass average molecular weight (Mw) = 30000 Resin] 100 parts by mass of component (b): esterification reaction product of 1 mol of 2,3,4,4′-tetrahydroxybenzophenone and 2.34 mol of 1,2-naphthoquinonediazide-5-sulfonyl chloride 27 .5 parts by mass (c) component: 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene 10 parts by mass (d) component: PGMEA 372 .5 parts by mass After the above components (a) to (d) are uniformly dissolved, 400 pp of BYK-310 (manufactured by Big Chemie) is used as a surfactant. m, and this was filtered using a membrane filter having a pore size of 0.2 μm to prepare a positive photoresist composition.
Using the obtained positive photoresist composition, a stepped resist pattern was formed by each of the resist pattern forming methods 1 to 4.
Each of the obtained stepped resist patterns was evaluated for heat resistance, dry etching resistance, and wet etching resistance. The results are shown in Table 1 below.

(Example 2)
A stepped resist pattern was formed in the same manner as in the Examples except that the composition of the positive photoresist composition was changed as follows, and the characteristics thereof were evaluated.
(A) Component: cresol novolak resin [m-cresol / p-cresol = 4/6 (molar ratio) mixed phenols and formaldehyde obtained by a condensation reaction by a conventional method, mass average molecular weight (Mw) = 30000 Resin] 100 parts by mass (b) Component: 1 mol of phenol compound represented by the above formula (IV) [bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) -3,4-dihydroxyphenylmethane] And esterification reaction product of 2,2-naphthoquinonediazide-5-sulfonyl chloride 27.5 parts by mass (c) Component: 1- [1- (4-hydroxyphenyl) isopropyl] -4- [ 1,1-bis (4-hydroxyphenyl) ethyl] benzene 10 parts by mass (d) Component: 372.5 parts by mass of PGMEA (a) to (d) After evenly dissolving the components, 400 ppm of BYK-310, (manufactured by Big Chemie) as a surfactant is added thereto, and this is filtered using a membrane filter having a pore size of 0.2 μm to obtain a positive photoresist composition. Prepared.

(Example 3)
A stepped resist pattern was formed in the same manner as in the Examples except that the composition of the positive photoresist composition was changed as follows, and the characteristics thereof were evaluated.
(A) Component: cresol novolak resin [m-cresol / p-cresol = 4/6 (molar ratio) mixed phenols and formaldehyde obtained by a condensation reaction by a conventional method, mass average molecular weight (Mw) = 15000 Resins] 100 parts by mass of component (b): esterification reaction product of 1 mol of 2,3,4,4′-tetrahydroxybenzophenone and 2.34 mol of 1,2-naphthoquinonediazide-5-sulfonyl chloride 27 .5 parts by mass (c) component: 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene 10 parts by mass (d) component: PGMEA 372 .5 parts by mass After the above components (a) to (d) are uniformly dissolved, 400 pp of BYK-310 (manufactured by Big Chemie) is used as a surfactant. m, and this was filtered using a membrane filter having a pore size of 0.2 μm to prepare a positive photoresist composition.

(Comparative Example 1)
A stepped resist pattern was formed in the same manner as in the Examples except that the composition of the positive photoresist composition was changed as follows, and the characteristics thereof were evaluated.
(A) Component: cresol novolak resin [m-cresol / p-cresol = 4/6 (molar ratio) mixed phenols and formaldehyde obtained by a condensation reaction by a conventional method, mass average molecular weight (Mw) = 8000 Resin] 100 parts by mass of component (b): esterification reaction product of 1 mol of 2,3,4,4′-tetrahydroxybenzophenone and 2.34 mol of 1,2-naphthoquinonediazide-5-sulfonyl chloride 27 .5 parts by mass (c) component: 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene 10 parts by mass (d) component: PGMEA 372 .5 parts by mass After the above components (a) to (d) were uniformly dissolved, 400 ppm of BYK-310 (manufactured by Big Chemie) was used as a surfactant. The mixture was mixed and filtered using a membrane filter having a pore size of 0.2 μm to prepare a positive photoresist composition.

(Comparative Example 2)
A stepped resist pattern was formed in the same manner as in the Examples except that the composition of the positive photoresist composition was changed as follows, and the characteristics thereof were evaluated.
(A) Component: cresol novolak resin [m-cresol / p-cresol = 4/6 (molar ratio) mixed phenols and formaldehyde obtained by a condensation reaction by a conventional method, mass average molecular weight (Mw) = 8000 resin] 100 parts by mass (b) component: 1 mol of phenol compound represented by the above formula (IV) [bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) -3,4-dihydroxyphenylmethane] And esterification reaction product of 2,2-naphthoquinonediazide-5-sulfonyl chloride 27.5 parts by mass (c) Component: 1- [1- (4-hydroxyphenyl) isopropyl] -4- [ 1,1-bis (4-hydroxyphenyl) ethyl] benzene 10 parts by mass (d) Component: 372.5 parts by mass of PGMEA The above components (a) to (d) Was dissolved uniformly, and 400 ppm of BYK-310 (manufactured by BYK-Chemie) as a surfactant was added thereto, and this was filtered using a membrane filter having a pore size of 0.2 μm to prepare a positive photoresist composition. did.

(Comparative Example 3)
A stepped resist pattern was formed in the same manner as in the Examples except that the composition of the positive photoresist composition was changed as follows, and the characteristics thereof were evaluated.
(A) Component: cresol novolak resin [m-cresol / p-cresol = 4/6 (molar ratio) mixed phenols and formaldehyde obtained by a condensation reaction by a conventional method, mass average molecular weight (Mw) = Resin of 5000] 100 parts by mass (b) Component: Esterification reaction product of 1 mol of 2,3,4,4′-tetrahydroxybenzophenone and 2.34 mol of 1,2-naphthoquinonediazide-5-sulfonyl chloride 27 .5 parts by mass (c) component: 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene 10 parts by mass (d) component: PGMEA 372 .5 parts by mass After the above components (a) to (d) were uniformly dissolved, 400 ppm of BYK-310 (manufactured by Big Chemie) was used as a surfactant. The mixture was mixed and filtered using a membrane filter having a pore size of 0.2 μm to prepare a positive photoresist composition.

It is sectional drawing which showed embodiment of the formation method of the resist pattern which concerns on this invention, and the formation method of a fine pattern to process order. It is sectional drawing which showed a part of manufacturing process of the conventional TFT array substrate. It is sectional drawing which showed a part of manufacturing process of the conventional TFT array substrate following the previous figure. It is sectional drawing which showed a part of manufacturing process of the conventional TFT array substrate following the previous figure. It is sectional drawing which showed a part of manufacturing process of the conventional TFT array substrate following the previous figure. It is sectional drawing which showed a part of manufacturing process of the conventional TFT array substrate following the previous figure. It is sectional drawing which showed a part of manufacturing process of the conventional TFT array substrate following the previous figure. It is sectional drawing which showed a part of manufacturing process of the conventional TFT array substrate following the previous figure. It is sectional drawing which showed a part of manufacturing process of the conventional TFT array substrate following the previous figure. It is sectional drawing which showed a part of manufacturing process of the conventional TFT array substrate following the previous figure. It is sectional drawing which showed a part of manufacturing process of the conventional TFT array substrate following the previous figure. It is sectional drawing which showed a part of manufacturing process of the conventional TFT array substrate following the previous figure. It is sectional drawing which showed a part of manufacturing process of the conventional TFT array substrate following the previous figure. It is sectional drawing which showed a part of manufacturing process of the conventional TFT array substrate following the previous figure. It is sectional drawing which showed a part of manufacturing process of the conventional TFT array substrate following the previous figure. It is sectional drawing which shows the example of a TFT array substrate.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Glass substrate 2 ... Gate electrode 3 ... 1st insulating film 4 '... 1st amorphous silica film 5' ... Etching stopper film 6 '... 2nd amorphous silica film 7' ... Metal film for source-drain electrode formation 10 ... Base R ... Stepped resist pattern r1 ... Thick part r2 ... Thin part

Claims (9)

(A) Step of forming a photoresist film on a substrate, (B) Stepwise resist pattern having a thick part and a thin part through a photolithography process including selective exposure through a halftone mask. And (D) a step of performing a post-bake treatment, and (C) a resist that does not have a step of performing a UV cure treatment between the step (B) and the step (D). A pattern forming method comprising:
A positive photoresist composition comprising (a) an alkali-soluble novolak resin having a polystyrene-reduced mass average molecular weight (Mw) of more than 8000 by gel permeation chromatography, (b) a naphthoquinonediazide group-containing compound, and (d) an organic solvent. To form the photoresist film using ,
As the base, a gate electrode, a first insulating film, a first amorphous silica film, an etching stopper film, a second amorphous silica film, and a metal film for forming a source / drain electrode are sequentially formed on a glass substrate from the glass substrate side. What is claimed is: 1. A method for forming a resist pattern, comprising using a multilayered structure .   The method for forming a resist pattern according to claim 1, wherein the alkali-soluble novolak resin has a polystyrene-reduced mass average molecular weight (Mw) of 10,000 or more.   3. The method for forming a resist pattern according to claim 1, wherein the temperature condition in the (D) post-bake treatment is 120 ° C. or less. After forming a stepped resist pattern having a thick portion and a thin portion by the method according to any one of claims 1 to 3, the substrate is etched using the stepped resist pattern as a mask. Then, (F) performing an ashing process (ashing process) on the stepped resist pattern to remove the thin part, and (G) removing the thin part and then using the thick part as a mask. A method of forming a fine pattern, comprising: performing an etching process on a substrate, and then (H) removing a thick portion of the stepped resist pattern. After forming a stepped resist pattern having a thick portion and a thin portion, (E) etching the substrate using the stepped resist pattern as a mask, and (F) ashing the stepped resist pattern. (G) After removing the thin portion, the substrate is etched using the thick portion as a mask, and then (H) the stepped shape is removed. A method for forming a fine pattern comprising a step of removing a thick portion of a resist pattern,
The stepwise resist pattern is formed by (A) forming a photoresist film on a substrate and (B) performing a photolithography process including selective exposure through a halftone mask. And (D) a step of performing post-baking treatment, and (C) UV between the step (B) and the step (D). Performed by the method of forming a stepped resist pattern that does not have a step of performing a curing process,
The stepwise resist pattern is formed by: (a) an alkali-soluble novolak resin having a polystyrene-reduced mass average molecular weight (Mw) exceeding 8000 by gel permeation chromatography, (b) a naphthoquinonediazide group-containing compound, and (d) an organic solvent. A method for forming a fine pattern, wherein the photoresist film is formed using a positive photoresist composition comprising After forming the stepped resist pattern which has a thick part and a thin part by the method as described in any one of Claims 1-3 , (E ') formation of the said source-drain electrode by using this stepped resist pattern as a mask After etching the metal film, the second amorphous silica film, the etching stopper film, and the first amorphous silica film, (F) an ashing process (ashing process) is performed on the stepped resist pattern. The thin portion is removed, and (G ′) the thin portion is removed, and then the source / drain electrode forming metal film and the second amorphous silica film are etched using the thick portion as a mask. A step of exposing the etching stopper film layer, and then (H) removing a thick portion of the stepped resist pattern. Forming method.   7. The fine pattern according to claim 6, wherein the etching process of the metal film for forming the source / drain electrodes is a wet etching process or a dry etching process, and the etching process of the second amorphous silica film is a dry etching process. Forming method. A method for producing a liquid crystal display element comprising a step of forming a pixel pattern on a glass substrate,
A method for manufacturing a liquid crystal display element, wherein a part of the pixel pattern is formed by the fine pattern forming method according to claim 4 .   After forming a fine pattern by the method according to claim 6 or 7, (I) a step of providing a second insulating film on the fine pattern, (J) a step of patterning the second insulating film by photolithography, (K) A method of manufacturing a liquid crystal display device, comprising: forming a transparent conductive film on the patterned second insulating film; and (L) patterning the transparent conductive film by photolithography.

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