CN100340925C - Erosion resistant pattern forming method, micro-pattern forming method using the same - Google Patents

Erosion resistant pattern forming method, micro-pattern forming method using the same Download PDF

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CN100340925C
CN100340925C CNB2004101003126A CN200410100312A CN100340925C CN 100340925 C CN100340925 C CN 100340925C CN B2004101003126 A CNB2004101003126 A CN B2004101003126A CN 200410100312 A CN200410100312 A CN 200410100312A CN 100340925 C CN100340925 C CN 100340925C
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resist pattern
mask
film
etching
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CN1629732A (en
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森尾公隆
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Tokyo Ohka Kogyo Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/36—Imagewise removal not covered by groups G03F7/30 - G03F7/34, e.g. using gas streams, using plasma
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/1259—Multistep manufacturing methods
    • H01L27/1288—Multistep manufacturing methods employing particular masking sequences or specially adapted masks, e.g. half-tone mask

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Abstract

The method for forming a resist pattern includes steps of: (A) forming a photoresist film on a substrate 10; (B) patterning the photoresist film into a pattern having a thick part r1 and a thin part r2 by way of photolithographic process including selective exposure; and (C) curing the resist with UV rays after patterning to form a step-like resist pattern R having the thick part r1 and the thin part r2.

Description

Resist pattern formation method, use the Micropicture formation method of this method
Technical field
The present invention relates to the formation method of resist pattern, the formation method of Micropicture of using this method and the manufacture method of liquid crystal display cells.
Background technology
In the manufacturing of the liquid crystal array substrate of liquid crystal display cells, use the photo-mask process that has utilized the photoresist tunicle.
Fig. 2～Figure 15 is the figure of example of the operation of expression α-Si (amorphous silica) shape tft array substrate of making structure shown in Figure 16.In this embodiment, at first as shown in Figure 2, on glass substrate 1, form gate electrode layer 2 '.
Then, go up at gate electrode layer 2 ' and to form the photoresist tunicle, make this photoresist tunicle form figure by photoetching process, this photoetching process comprises by mask and the operation that selectivity is exposed as shown in Figure 3, forms resist pattern R1 (the 1st photo-mask process).
Then, the resist pattern R1 that obtains is carried out etching as mask to gate electrode layer 2 ', form as shown in Figure 4 gate electrode 2 by removing resist pattern R1 then.
Then, as shown in Figure 5, on the glass substrate 1 that forms gate electrode 2, form the 1st dielectric film 3, and then form the 1st α-Si layer 4 ' and etching block film 5 ' in the above in order.
Go up at etching block film 5 ' and to form the photoresist tunicle, make this photoresist tunicle form figure by photoetching process, this photoetching process comprises by mask and the operation that selectivity is exposed as shown in Figure 6, forms resist pattern R2 (the 2nd photo-mask process).
Then, the resist pattern R2 that obtains is carried out etching as mask to the 1st α-Si layer 4 ' and etching block film 5 ', then by remove resist pattern R2 form as shown in Figure 7 the 1st α-Si layer 4 and the duplexer of etching block film 5.
As shown in Figure 8, forming the 2nd α-Si layer 6 ' and source-drain electrode thereon in order forms with metal film 7 '.
Then, go up formation photoresist tunicle at this metal film 7 ', make this photoresist tunicle form figure by photoetching process, this photoetching process comprises by mask and the operation that selectivity is exposed forms resist pattern R3 (the 3rd photo-mask process) as shown in Figure 9.
Then, the resist pattern R3 that obtains is carried out etching as mask to metal film 7 ' and the 2nd α-Si layer 6 ', by removing resist pattern R3, as shown in figure 10, on etching block film 5, form patterned the 2nd α-Si layer 6 and source electrode and gate electrode 7 then.
Then, as shown in figure 11, on glass substrate 1, form the 2nd dielectric film 8 '.
Then, go up formation photoresist tunicle at the 2nd dielectric film 8 ', make this photoresist tunicle form figure by photoetching process, this photoetching process comprises by mask and the operation that selectivity is exposed forms resist pattern R4 (the 4th photo-mask process) as shown in figure 12.
Then, the resist pattern R4 that obtains is carried out etching as mask to the 2nd dielectric film 8 ',, as shown in figure 13, form the 2nd dielectric film 8 that is patterned into shape with contact hole then by removing resist pattern R4.
Then, as shown in figure 14, on glass substrate 1, form nesa coating 9 '.
Then, go up formation photoresist tunicle at this nesa coating 9 ', make this photoresist tunicle form figure by photoetching process, this photoetching process comprises by mask and the operation that selectivity is exposed forms resist pattern R5 (the 5th photo-mask process) as shown in figure 15.
Then, the resist pattern R5 that obtains is carried out etching as mask to nesa coating 9 ', then by removing resist pattern R5, as shown in figure 16, formation has the nesa coating 9 of figure, thereby obtains the liquid crystal array substrate.
Make the method for liquid crystal array substrate through this operation, carry out the photo-mask process (the 1st～the 5th photo-mask process) that uses photomask to carry out the selectivity exposure 5 times altogether.
But, in recent years, the low price of strong request liquid crystal display cells is also being sought the simplification of manufacturing process for this reason, and the consumption of control resist etc.
Therefore, in order to respond this demand, the step resist pattern different according to the different used thicknesses in field thus, once proposed to have used with 1 time photo-mask process the method for 2 times photo-mask process in the past.In the method, the step resist pattern is carried out etching as mask, then by utilizing its thickness difference, will not carry out photo-mask process and the flat shape deformable members that makes this step resist pattern is used as mask once more, to carry out etching.
According to said method, can reduce the number of times of implementing photo-mask process in theory, so can control the consumption of resist thus, also can simplify operation, be effective in the manufacturing of the liquid crystal display cells of cheapness so wish it.
But even preferred anticorrosive additive material forms this step resist pattern in the use liquid crystal display cells manufacturing in the past, elching resistant and thermotolerance are abundant inadequately, so realize relatively difficulty of this method.
Specifically, as mentioned above,, need it to have high elching resistant, but it is relatively more difficult to form this step resist pattern with high elching resistant because the step resist pattern all uses as etched mask before its distortion and after the distortion.
In addition, in order to make employed resist pattern tolerance etching work procedure and injection process in the manufacturing of liquid crystal display cells, sometimes implementing the back baking handles to improve thermotolerance, but in liquid crystal display cells manufacturing in the past preferred anticorrosive additive material inexpensive and have a highly sensitive reverse side, the trend that the thermotolerance deterioration occurs, so make the resist pattern of step flaw occur by back baking processing, thereby be difficult to keep the different shape of thickness.
Summary of the invention
The invention that the present invention In view of the foregoing finishes just, its purpose are, provide a kind of elching resistant and excellent heat resistance also can form the formation method of the resist pattern of step resist pattern.
In addition, the present invention also aims to, the formation method of Micropicture of the formation method of having used resist pattern of the present invention and the manufacture method of using the liquid crystal display cells of this figure are provided.
In order to achieve the above object, the formation method of resist pattern of the present invention has: (A) make above-mentioned photoresist tunicle form the operation of the graphics shape with heavy section and thinner wall section through containing the photo-mask process of selective exposure and (C) carrying out above-mentioned figure and carrying out UV after forming and solidify and handle and formation has the operation of the step resist pattern of heavy section and thinner wall section at the operation that forms the photoresist tunicle on the matrix, (B).
The formation method of Micropicture of the present invention preferably contains (D) and further carry out the operation that the back baking is handled after having carried out above-mentioned UV curing processing.
Formation method about Micropicture of the present invention, as above-mentioned matrix, preferably have from glass substrate one side and begin in order gate electrode, the 1st dielectric film, the 1st amorphous silica film, etching block film, the 2nd amorphous silica film and source-drain electrode are formed the member that is stacked in the sandwich construction that glass substrate forms with metallic diaphragm.
Formation method about Micropicture of the present invention, after forming above-mentioned step resist pattern, the preferred operation that further has is: (E) this step resist pattern is carried out etch processes as mask to above-mentioned matrix, then, (F) this step resist pattern being carried out ashing (ashing) handles, remove above-mentioned thinner wall section, (G) after removing above-mentioned thinner wall section, heavy section is implemented etch processes as mask to above-mentioned matrix, and (H) removes the operation of the heavy section of above-mentioned step resist pattern subsequently.
Perhaps, formation method about Micropicture of the present invention, after the formation method of the resist pattern of the present invention of the matrix that has above-mentioned multilayer structure making by use forms above-mentioned step resist pattern, preferably further having (E ') forms this step resist pattern and uses metal film as mask and to above-mentioned source-drain electrode, above-mentioned the 2nd amorphous silica film, above-mentioned etching block film, and above-mentioned the 1st amorphous silica film carries out etch processes, then, (F) this step resist pattern being carried out ashing (ashing) handles, remove above-mentioned thinner wall section, (G ') after removing above-mentioned thinner wall section, heavy section is formed with metal film and above-mentioned the 2nd amorphous silica film enforcement etch processes above-mentioned source-drain electrode as mask, stop rete to expose above-mentioned etching, (H) removes the operation of the heavy section of above-mentioned step resist pattern subsequently.
About the formation method of Micropicture of the present invention, above-mentioned source-drain electrode is formed preferred wet etch process of etch processes or the dry-etching of using metal film handle, the etch processes preferred dry etch processes of last several the 1st amorphous silica films.
The manufacture method of liquid crystal display cells of the present invention, be manufacture method, form the part of above-mentioned pixel graphics by the formation method of Micropicture of the present invention with liquid crystal display cells of the operation that on glass substrate, forms pixel graphics and make the liquid crystal array substrate.
In addition, the manufacture method of liquid crystal display cells of the present invention, be after the formation method of the resist pattern of the present invention of the matrix that has above-mentioned multilayer structure making by use forms Micropicture, preferably further have (I) and make the 2nd dielectric film form operation, (L) of forming nesa coating on the operation of figure, the 2nd dielectric film that (K) forming figure by photoetching at the operation that the 2nd dielectric film is set on this Micropicture, (J) to make nesa coating form the operation of figure by photoetching.
According to the formation method of resist pattern of the present invention, solidify the step resist pattern that can form elching resistant, thermotolerance is good and has good shape stability by after the photoresist tunicle forms figure, implementing UV.
In addition, in the manufacturing of liquid crystal display cells, manufacturing process compares with semiconductor, and the resist consumption is significantly big to be quantized, and in addition, for high productivity ground makes the large substrate commercialization, the raising turnout is absolutely necessary.In the past, though anticorrosive additive material that for example will optionally use low-molecular-weight resin etc. is inexpensive and highly sensitive anticorrosive additive material is used for this purposes, but the trend that the thermotolerance deterioration occurs, so flaw appears in the step resist pattern of handling through baking later, thereby is difficult to keep the different shape of thickness.According to the present invention,, also can form elching resistant, the good step resist pattern of thermotolerance even use this inexpensive and highly sensitive anticorrosive additive material.
Formation method according to Micropicture of the present invention, the elching resistant of step resist pattern is good, so after this step resist pattern is carried out etching as mask and to matrix, the member that the thinner wall section of removing this step resist pattern by ashing (ashing) processing can be formed is once more as mask, thereby matrix is carried out etching, use photomask the photoresist tunicle to be carried out the number of times of the photo-mask process of figure formation so can reduce.
Therefore, can control the consumption of photoresist, also can cut down the expense of the high photomask of relative valency, and then operation is simplified.
Manufacture method according to liquid crystal display cells of the present invention, can on glass substrate, form pixel graphics and reduce the number of times of making the photo-mask process in the liquid crystal array substrate operation, so can realize thus, the inhibition of photoresist consumption, the reduction that photomask uses.In addition, manufacturing process also can simplify, so be effective to making inexpensive liquid crystal display cells.
Description of drawings
Figure 1A～Fig. 1 G is the sectional view of embodiment of representing the formation method of the formation method of resist pattern of the present invention and Micropicture by process sequence.
Fig. 2 is the sectional view of a part of representing the manufacturing process of liquid crystal array substrate in the past.
Fig. 3 is the sectional view of the part of the manufacturing process of the liquid crystal array substrate in the past of figure before expression continues.
Fig. 4 is the sectional view of the part of the manufacturing process of the liquid crystal array substrate in the past of figure before expression continues.
Fig. 5 is the sectional view of the part of the manufacturing process of the liquid crystal array substrate in the past of figure before expression continues.
Fig. 6 is the sectional view of the part of the manufacturing process of the liquid crystal array substrate in the past of figure before expression continues.
Fig. 7 is the sectional view of the part of the manufacturing process of the liquid crystal array substrate in the past of figure before expression continues.
Fig. 8 is the sectional view of the part of the manufacturing process of the liquid crystal array substrate in the past of figure before expression continues.
Fig. 9 is the sectional view of the part of the manufacturing process of the liquid crystal array substrate in the past of figure before expression continues.
Figure 10 is the sectional view of the part of the manufacturing process of the liquid crystal array substrate in the past of figure before expression continues.
Figure 11 is the sectional view of the part of the manufacturing process of the liquid crystal array substrate in the past of figure before expression continues.
Figure 12 is the sectional view of the part of the manufacturing process of the liquid crystal array substrate in the past of figure before expression continues.
Figure 13 is the sectional view of the part of the manufacturing process of the liquid crystal array substrate in the past of figure before expression continues.
Figure 14 is the sectional view of the part of the manufacturing process of the liquid crystal array substrate in the past of figure before expression continues.
Figure 15 is the sectional view of the part of the manufacturing process of the liquid crystal array substrate in the past of figure before expression continues.
Figure 16 is the sectional view of the example of expression liquid crystal array substrate.
Embodiment
＜photo-corrosion-resisting agent composition 〉
The photo-corrosion-resisting agent composition that is used to form the photoresist tunicle is not particularly limited, can uses to be used for the anticorrosive additive material that liquid crystal display cells is made up to now.
For example, the positive light anti-etching agent composition that can preferably use is: with respect to (A) alkali soluble resin 100 mass parts, contain represented phenolic compounds 5～25 mass parts of (B) following general formula (I), with respect to (A) composition and (B) gross mass 100 mass parts of composition, contain from the represented quinone two nitrine carboxylates (photographic composition 2) of the represented quinone two nitrine carboxylates (photographic composition 1) of (C) following general formula (III) and following general formula (V), select at least a, and its content range is 15～40 mass parts, and then contains (D) organic solvent.
Figure C20041010031200111
[in the formula, R 1～R 8Represent the alkyl of hydrogen atom, halogen atom, carbon number 1～6, the alkoxy of carbon number 1～6 or the naphthenic base of carbon number 3～6 respectively independently; R 10, R 11The alkyl of representing hydrogen atom or carbon number 1～6 respectively independently; R 9Can be the alkyl of hydrogen atom, carbon number 1～6, this moment, Q has the alkyl of hydrogen atom, carbon number 1～6 or with following chemical formula (II)
Figure C20041010031200112
(in the formula, R 12And R 13Represent the alkyl of hydrogen atom, halogen atom, carbon number 1～6, the alkoxy of carbon number 1～6 or the naphthenic base of carbon number 3～6 respectively independently; C represents integer 1～3.) expression residue, perhaps, Q can and R 9Terminal bonding, at this moment, Q and R 9, and Q and R 9Between carbon atom represent the naphthenic base of carbon number 3～6 together; A, b represent integer 1～3; D represents integer 0～3; When a, b or d are 3, respectively as the compound that does not have R3, R6 or R8; N represents integer 0～3.]
Figure C20041010031200113
[in the formula, R 1～R 8Represent the alkyl of hydrogen atom, halogen atom, carbon number 1～6, the alkoxy of carbon number 1～6 or the naphthenic base of carbon number 3～6 respectively independently; R 10, R 11The alkyl of representing hydrogen atom or carbon number 1～6 respectively independently; R 9Can be the alkyl of hydrogen atom, carbon number 1～6, this moment, Q be the alkyl or the following chemical formula (IV) of hydrogen atom, carbon number 1～6
Figure C20041010031200121
(in the formula, R 12And R 13Represent the alkyl of hydrogen atom, halogen atom, carbon number 1～6, the alkoxy of carbon number 1～6 or the naphthenic base of carbon number 3～6 respectively independently; C represents integer 1～3.), perhaps, Q can and R 9Terminal bonding, at this moment, Q and R 9, and Q and R 9Between carbon atom represent the naphthenic base of carbon number 3～6 together; D represents hydrogen atom or 1 independently, 2-naphthoquinones two nitrine-5-sulfonyl, at least one expression 1 among the D, 2-naphthoquinones two nitrine-5-sulfonyl; A, b represent integer 1～3; D represents integer 0～3; When a, b or d are 3, respectively as the compound that does not have R3, R6 or R8; N represents integer 0～3.]
Figure C20041010031200122
(in the formula, D represents hydrogen atom or 1 independently, 2-naphthoquinones two nitrine-5-sulfonyl, at least one expression 1 among the D, 2-naphthoquinones two nitrine-5-sulfonyl.)
About (A) composition (alkali soluble resin):
Alkali soluble resin as (A) composition is not particularly limited, in positive light anti-etching agent composition, forms material, can from common operable material, select arbitrarily as tunicle.For example, can be exemplified as the tunicle of positive light anti-etching agent composition and form with resin and the polymkeric substance of well-known phenolics, acryl resin, styrene and acrylic acid multipolymer, hydroxy styrenes, polyvinylphenol, poly-Alpha-Methyl vinylphenol etc.Wherein, especially preferably use phenolics, wherein, preferably need not swelling and easily be dissolved in alkaline aqueous solution and the good thermoplastic phenolic varnish gum of development.
As the example of phenolics, can list the condensation reaction products, vinyl phenol base polymer, isopropenyl phenol polymer of condensation reaction products, phenols and the ketone of phenols and aldehydes, their hydrogenation reaction product etc. of phenolics.
Phenols as forming above-mentioned phenolics can list as phenol; Cresols classes such as metacresol, paracresol, orthoresol; 2,3-xylenols, 2,5-xylenols, 3,5-xylenols, 3, dimethylbenzene phenols such as 4-xylenols; M-ethylphenol, paraethyl phenol, o-ethyl phenol, 2,3,5-pseudocuminol, 2,3,5-triethyl phenol, 4-tert-butyl phenol, 3-tert-butyl phenol, 2-tert-butyl phenol, the 2-tert-butyl group-4-methylphenol, the 2-tert-butyl group-alkyl benzene phenols such as 5-methylphenol; P methoxy phenol, meta-methoxy phenol, to thanatol, m-oxethyl phenol, to alkoxy benzene phenols such as propoxyl group phenol, propoxyl group phenol; Adjacent isopropenyl phenol, to isopropenyl phenol, 2-methyl-4-isopropenyl phenol, 2-ethyl-isopropenylbenzene phenols such as 4-isopropenyl phenol; Aryl phenol classes such as phenylphenol; 4, poly-hydroxy benzenes phenols such as 4 '-dihydroxybiphenyl, bisphenol-A, resorcinol, p-dihydroxy-benzene, pyrogallol etc.Them can be used separately, also two or more uses can be made up.In the middle of these phenols, preferred especially metacresol, paracresol, 2,5 xylenols, 3,5-xylenols, 2,3,5-pseudocuminol.
As above-mentioned aldehydes, can list as formaldehyde, paraformaldehyde, three  alkane, acetaldehyde, propionic aldehyde, butyraldehyde, trimethyl-acetaldehyde, acryl aldehyde, crotonaldehyde, hexamethylene aldehyde, furfural, furylacrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-benzenpropanal, β-Ben Bingquan, salicylaldhyde, m-hydroxybenzaldehyde, parahydroxyben-zaldehyde, o-methyl-benzene formaldehyde, a tolyl aldehyde, p-tolyl aldehyde, o-chlorobenzaldehyde, m chlorobenzaldehyde, 4-chloro-benzaldehyde, cinnamic acid etc.Them can be used separately, also two or more uses can be made up.In the middle of these aldehydes, from the viewpoint of easy acquisition, preferred formaldehyde, but in order to improve thermotolerance, special preferred compositions is used hydroxy benzaldehyde class and formaldehyde.
As above-mentioned ketone, can list as acetone, methyl ethyl ketone, diethyl ketone, diphenylmethanone etc.Them can be used separately, also two or more uses can be made up.In the middle of the combination of phenols and ketone, the combination of preferred especially pyrogallol and acetone.
The condensation reaction products of phenols and aldehydes or ketone can be made by the known method that has acidic catalyst to exist.Acidic catalyst as this moment can use hydrochloric acid, sulfuric acid, formic acid, oxalic acid, p-toluenesulfonic acid etc.The condensation reaction products that obtains thus has good thermotolerance by the material of implementing the low molecular domains that processing such as classification tell, so preferably.Processing such as classification are in good solvent, as alcohol such as methyl alcohol, ethanol by the resin dissolves that will obtain by condensation reaction, ketone such as acetone, methyl ethyl ketone, or in ethylene glycol monoethyl ether acetate, the tetrahydrofuran etc., then be injected in the water and methods such as its precipitation are carried out.
In above-mentioned material, particularly preferably in contain in the full phenols repetitive 60 moles of paracresol class repetitives more than the % and contain 30 moles of metacresol class repetitives more than the % and polystyrene conversion weight-average molecular weight (Mw) be 2000～8000 novolac resin.
When paracresol class repetitive during less than 60 moles of %, the change of sensitivity of the temperature inequality when occurring at heat treated easily, in addition, when metacresol class repetitive during less than 30 moles of %, sensitivity has the trend of deterioration, so not preferred.
Also have, also can contain other phenols repetitive such as dimethylbenzene phenols repetitive, trimethylbenzene phenols repetitive, the novolac resin of 2 group categories that most preferably are made of 60～70 moles of % of paracresol class repetitive, 40～30 moles of % of metacresol class repetitive but, preferably 2 nucleomes (the condensation product molecule that 2 the phenol nuclears are arranged) content as phenols is the less novolac resin of low-molecular-weight body burden of the phenols below 10% in GPC (gel permeation chromatography) method.This is because the distillation and pollute the top board etc. of stove in the preliminary drying of high temperature (for example 130 ℃) or back baking of above-mentioned 2 nucleomes, and then pollutes the glass substrate that has applied resist, becomes the reason that its effective rate of utilization reduces.
About (B) composition (sensitizer)
As (B) composition, the preferred phenolic compound that uses by above-mentioned general formula (I) expression.
Example as (B) composition, can list three (4-hydroxyphenyl) methane, two (4-hydroxy-3-methyl phenyl)-2-hydroxyphenyl methane, two (4-hydroxyls-2,3, the 5-trimethylphenyl)-2-hydroxyphenyl methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-4-hydroxyphenyl methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-3-hydroxyphenyl methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-2-hydroxyphenyl methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-4-hydroxyphenyl methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-3-hydroxyphenyl methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-2-hydroxyphenyl methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-3,4-dihydroxyphenyl methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-3,4-dihydroxyphenyl methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-2,4-dihydroxyphenyl methane, two (4-hydroxyphenyl)-3-methoxyls-4-hydroxyphenyl methane, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-4-hydroxyphenyl methane, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-3-hydroxyphenyl methane, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-2-hydroxyphenyl methane, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-3,4-dihydroxyphenyl methane, 1-[1-(4-hydroxyphenyl) isopropyl]-4-[1, two (4-hydroxyphenyl) ethyls of 1-] benzene, 1-[1-(3-methyl-4-hydroxyphenyl) isopropyl]-4-[1, two (3-methyl-4-hydroxyphenyl) ethyls of 1-] benzene, 2-(2,3,4-three hydroxyphenyl)-2-(2 ', 3 ', 4 '-three hydroxyphenyl) propane, 2-(2, the 4-dihydroxyphenyl)-2-(2 ', 4 '-dihydroxyphenyl) propane, 2-(4-hydroxyphenyl)-2-(4 '-hydroxyphenyl) propane, 2-(3-fluoro-4-hydroxyphenyl)-2-(3 '-fluoro-4 '-hydroxyphenyl) propane, 2-(2, the 4-dihydroxyphenyl)-2-(4 '-hydroxyphenyl) propane, 2-(2,3,4-three hydroxyphenyl)-2-(4 '-hydroxyphenyl) propane, 2-(2,3,4-three hydroxyphenyl)-2-(4 '-hydroxyl-3 ', 5 '-3,5-dimethylphenyl) propane, two (2,3,4-three hydroxyphenyl) methane, two (2, the 4-dihydroxyphenyl) methane, 2,3,4-three hydroxyphenyl-4 '-hydroxyphenyl methane, 1,1-two (4-hydroxyphenyl) cyclohexane, 2, two [1-(4-hydroxyphenyl) the isopropyl]-5-hydroxyl phenols of 4-etc.
Wherein, because the sensitizing effect is especially good, so preferred two (4-hydroxy-3-methyl phenyl)-2-hydroxyphenyl methane, two (4-hydroxyl-2,3, the 5-trimethylphenyl)-2-hydroxyphenyl methane, 2, two [1-(4-hydroxyphenyl) the isopropyl]-5-hydroxyl phenols, 1 of 4-, 1-two (4-hydroxyphenyl) cyclohexane, 1-[1-(4-hydroxyphenyl) isopropyl]-4-[1, two (4-hydroxyphenyl) ethyls of 1-] benzene etc.
In the manufacturing field of liquid crystal display cells, the raising of turnout is very large problem, but by cooperating this phenolic compound, reaches high sensitivityization and helps to improve turnout, so preferred.
In addition, by cooperating this phenolic compound, form solid surperficial indissoluble layer on etchant resist, so the film wear extent of the etchant resist of unexposed portion when developing is less, control is because of the appearance of the development inequality of the difference generation of development time, so preferred.
In this phenolic compounds, with the compound of following formula (VI) expression (1-[1-(4-hydroxyphenyl) isopropyl]-4-[1, two (4-hydroxyphenyl) ethyls of 1-] benzene) and with following formula (VII) represent (two (2,3,5-trimethyl-4-hydroxyphenyl)-and 2-hydroxyphenyl methane) in high sensitivityization, high residual film ratioization and linear improving on the good this point of effect, preferred especially.
Figure C20041010031200161
When cooperating (B) composition, with respect to alkali soluble resin 100 mass parts as (A) composition, its content is for to select in the scope of 5～25 mass parts, preferred 10～20 mass parts.When not enough this scope, can't obtain the effect of improving of enough high sensitivityization, high residual film ratioization, when surpassing this scope, easily the residue thing appears on the substrate surface after the development, and in addition, raw materials cost also raises, so not preferred.
About (C) composition (photographic composition):
Preferred use from the represented quinone two nitrine carboxylates (photographic composition 2) of the represented quinone two nitrine carboxylates (photographic composition 1) of above-mentioned general formula (III) and above-mentioned general formula (V), select at least a, particularly use this photographic composition 1 and photographic composition 2, even using 500 * 600mm by mixing 2The technology of large-size glass substrate in, also can provide macroscopic property (screening characteristics, heat uneven characteristic, the uneven characteristic of developing) good anticorrosive additive material.
Also have, the average esterification yield of photographic composition 1 is preferred 40～60%, and more preferably 45～55%.When less than 40% the time, the film wearing and tearing after occurring easily developing reduce rate of film build easily.When surpassing 60%, the trend of the obvious deterioration of sensitivity is arranged.
As this photographic composition 1; according to compound (two (2-methyl-4-hydroxyl-5-cyclohexyl benzene)-3 with following formula (VIII) expression; 4-dihydroxyphenyl methane) 1; the quinone two nitrine carboxylates that 2-naphthoquinones two nitrine-the 5-sulfonyl compound forms are preferred regulating on relatively inexpensive and sensitivity, sharpness, the linear good resist composition this point.Wherein, esterification yield 50% most preferably.
Figure C20041010031200171
On the other hand, as photographic composition 2, preferably according to using 2,3,4 of following formula (IX) expression, 1 of 4 '-dihydroxy benaophenonel, the quinone two nitrine carboxylates that 2-naphthoquinones two nitrine-the 5-sulfonyl compound forms.Wherein, the material of preferred average esterification yield 50～70%, more preferably 55～65%.When less than 50% the time, the film wearing and tearing after occurring easily developing reduce residual film ratio easily.On the other hand, when surpassing 70%, the trend that has bin stability to reduce.This photographic composition 2 is preferred regulating on the resist composition this point that price is very cheap and sensitivity is good.Wherein, the material of esterification yield 59% most preferably.
Figure C20041010031200172
(C) photographic composition can also use other quinone two nitrine carboxylates except can using above-mentioned photographic composition 1,2.
The use amount of above-mentioned other quinone two nitrine carboxylates is preferably in (C) photographic composition below the 30 quality %, below 25 quality %.
About the blending ratio of photographic composition 1 and 2, with respect to 50 mass parts of photographic composition 1, preferred photographic composition 2 is 40～60 mass parts, in the scope particularly preferably in 45～55 mass parts.
When the use level of photographic composition 2 was less than this scope, sensitivity had the trend of deterioration, and when more than this scope, the sharpness of resist composition, linearity have the trend of deterioration.
With respect to as the alkali soluble resin of (A) composition and (B) total of composition measure 100 mass parts, (C) use level of composition is chosen as in the scope of 15～40 mass parts, preferred 20～30 mass parts.When the use level of (C) composition inadequately during above-mentioned scope, can't obtain the image of faithful to figure, and replicability reduces also.On the other hand, when the use level of (C) composition surpassed above-mentioned scope, sensitivity and sharpness deterioration in addition, occurred the trend of residue thing after development treatment.
This photo-corrosion-resisting agent composition preferably is dissolved in (A)～(C) composition and various adding ingredient as following (D) composition of organic solvent and uses with the form of solution.
About (D) composition (organic solvent):
As the example of preferred organic, can list ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone; Polyalcohols and derivants thereof such as ethylene glycol, propylene glycol, diglycol, ethylene glycol acetate, propylene glycol monoacetate, diglycol monotertiary acetic acid esters or their monomethyl ether, single ethylether, single propyl ether, single-butyl ether or single phenyl ether; The cyclic ethers class of similar two  alkane; And ester class such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxypropionic acid methyl esters, ethoxyl ethyl propionate.Can use them separately, also can mix more than 2 kinds and use.
Wherein, propylene glycol monomethyl ether (PGMEA) gives photo-corrosion-resisting agent composition good screening characteristics, and gives the resist tunicle on the large-size glass substrate good film thickness uniformity, so preferred.
Most preferably PGMEA is used as neat solvent, but the solvent except that PGMEA also can mix use with it.As this solvent, can be exemplified as ethyl lactate, gamma-butyrolacton, propylene glycol single-butyl ether etc.
When using ethyl lactate, preferably in being the scope of 0.1～10 times of amount, preferred 1～5 times of amount, the mass ratio with respect to PGMEA cooperates.
In addition, when using gamma-butyrolacton, preferably in being the scope of 0.01～1 times of amount, preferred 0.05～0.5 times of amount, the mass ratio with respect to PGMEA cooperates.
In the manufacturing field of liquid crystal display cells, usually need the resist tunicle to be formed on the glass substrate with 0.5～2.5 μ m, the particularly thickness of 1.0～2.0 μ m, preferably use these organic solvents for this reason, with the total amount of above-mentioned (A)～(C) composition in the composition with respect to the gross mass of composition be adjusted to below the 30 quality %, preferred 20～28 quality %, with as screening characteristics liquid crystal display device with excellent manufacturing anticorrosive additive material.
Also consider the amount of arbitrarily used following (E) composition this moment, and with respect to the gross mass of composition, the use amount of solvent (D) is 65～85 quality %, preferred 70～75 quality %.
About (E) composition (other adjuvants):
As other compositions, can in the scope that does not influence purpose of the present invention, add following additives, promptly be used to the dizzy ultraviolet light absorber that disappears, as 2,2 ', 4,4 '-tetrahydroxybenzophenone, 4-dimethylamino-2 ', 4 '-dihydroxy benaophenonel, 5-amino-3-methyl isophthalic acid-phenyl-4-(hydroxy benzenes azo group) pyrazoles, 4-dimethylamino-4 '-hydroxyazobenzene, 4-diethylin-4 '-ethoxy azobenzene, 4 '-diethylin azobenzene, curcumin etc.; Or be used to prevent the surfactant of streak, as Florade FC-430, FC-431 (trade name, Sumitomo 3M (strain) system), Efftop EF122A, EF122B, EF122C, EF126 (trade name, TokemProduct (strain) system) waits fluorine class surfactant, stable storage agent such as benzoquinones, naphthoquinones, p-toluenesulfonic acid and then can also add the adjuvant that addition resin, plastifier, stabilizing agent, contrast improver etc. are habitually practised in case of necessity.
Below, enumerate and be applied to the example that liquid crystal display cells is made, with reference to Figure 1A～Fig. 1 G, the formation method of resist pattern of the present invention and the embodiment of the formation method of the Micropicture that has used this method are described.
At first.Prepare matrix.Matrix of the present invention is not particularly limited, but on using substrate, be laminated with more than 2 layers be used for the matrix of etched layer the time, can effectively obtain effect of the present invention, so preferred.
When making liquid crystal display cells, as matrix 10, for example, shown in Figure 1A, use to have on glass substrate 1 to begin to stack gradually the member that gate electrode the 2, the 1st dielectric film the 3, the 1st amorphous silica film 4 ', etching block film 5 ', the 2nd amorphous silica film 6 ' and source-drain electrode form the sandwich construction that forms with metal film 7 ' from glass substrate 1 one sides.The figure of gate electrode 2 forms and can carry out according to the step (comprising the 1st photo-mask process) of above-mentioned Fig. 2～Fig. 4.
Size to glass substrate is not particularly limited, and also can form 500 * 600mm 2More than, 550～650mm particularly 2Above large substrate.
Gate electrode 2 is to use as conductive materials such as aluminium (Al), chromium (Cr), titanium (Ti) or molybdenum metals such as (Mo) and forms.
The 1st dielectric film 3 for example is by SiN xForm.
Etching block film 5 ' for example is by SiN xForm.
It for example is the stacked film formation that formed by stacked titanium (Ti) and aluminium (Al) and titanium (Ti) in order that source-drain electrode forms with metal film 7 '.
(A) at first, on matrix 10, form photoresist tunicle R '.Specifically, the above-mentioned photo-corrosion-resisting agent composition of coating forms photoresist tunicle R ' by carry out heat drying (preliminary drying) under about 100～140 ℃ on matrix 10.
About preferred 1.0～3.0 μ m of the thickness of photoresist tunicle R '.Be uneven and can be uneven to this and carry out the viewpoint of the good exploring of shape from can form this in the exposure of appropriateness, the scope of time shutter, preferably the thickness with photoresist tunicle R ' is located in this scope.
(B) then, through photo-mask process, shown in Figure 1B, photoresist tunicle R ' forms the graphics shape with heavy section r1 and thinner wall section r2.Specifically, for example the mask (graticule) that is provided with transmitance by reticulate pattern mask etc. carries out the selectivity exposure to photoresist tunicle R ', then develops, washes, and can form the resist pattern because of the different shape of regional difference thickness thus.(the 2nd photo-mask process) (C) forms after the figure, carries out UV (ultraviolet ray) and solidifies processing, obtains the step resist pattern R shown in Figure 1B.
Because the ashing (ashing) by is afterwards handled and is only removed thinner wall section r2 and with the residual heavy section r1 of the thickness of needs, so about preferred 0.5～1.5 μ m of the heavy section r1 of step resist pattern R and the thickness difference of thinner wall section r2, preferred scope is about 0.7～1.3 μ m.
Can use known method to carry out UV solidifies.For example, use known ultraviolet lamp, the resist pattern that forms figure is carried out comprehensively ultraviolet ray irradiation.
About the ultraviolet irradiation condition, for UV solidifies the shape of resist pattern is deformed, obtain the step resist pattern R that elching resistant is good and thermotolerance is good, preferred use main output particularly from the ultraviolet light source of ultraviolet ray, the particularly wavelength about 200～500nm of the wavelength (about wavelength 100～700nm) of Deep UV zone to visible region, with about 1000～50000mJ/cm 2Exposure shine.Preferred exposure is 2000～15000mJ/cm 2About.Can control exposure by the ultraviolet intensity and the irradiation time of irradiation.
Also have, when carrying out UV when solidifying (irradiation), in order gauffer not occur in irradiation portion, preferably the temperature rising that rapid irradiation or irradiation are caused is controlled.
(D) after UV solidifies, can carry out the back baking.Specifically, this back baking processing is to implement heat treated under 100～170 ℃ the temperature about 3～10 minutes.Preferred heating condition is about 120～130 ℃, 4～6 minutes.
It not is necessary that this back baking is handled, but can further improve the thermotolerance of step resist pattern R by baking after carrying out.In addition, handle, can improve the connecting airtight property of step resist pattern R and matrix 10, so it is especially effective that wet etch process is obtained height endurability by the back baking.Wherein, solidify the thermotolerance that processing improves step resist pattern R, so in back baking operation, needn't worry to occur the distortion of figure by UV.
Wherein, as required, this UV solidifies processing and the back baking is handled also and can be carried out once more after ashing (ashing) processing of the step resist pattern R in (F) described later operation.
(E) shown in Fig. 1 C, the step resist pattern R that so forms as mask, is carried out etching to the metal film 7 ' of matrix 10.Can use well-known gimmick to carry out the etching of metal film 7 '.General use wet etching, but also can be the dry-etching method.
Then, shown in Fig. 1 D, same step resist pattern R as mask, is carried out etching to the 2nd amorphous silica film 6 ' and etching block film 5 ' and the 1st amorphous silica film 4 ' below it that exposes because of the etching of above-mentioned metal film 7 '.Can use well-known gimmick to carry out the etching of these layers.Generally can use the dry-etching method.By the step resist pattern R here being used as the etching of mask, form etching block film 5 and the 1st amorphous silica layer 4.
(F) subsequently, step resist pattern R is implemented ashing (ashing) handle, shown in Fig. 1 E, remove thinner wall section r2.Can use well-known gimmick to carry out ashing (ashing) handles.
When step resist pattern R being carried out ashing (ashing) and handle, the film wearing and tearing appear in heavy section r1 and thinner wall section r2 simultaneously, almost completely remove thinner wall section r2, become the metal film 7 ' that exposes below it and the residual state that heavy section r1 is arranged.Under this state, can only remove thinner wall section r2 by stopping ashing (ashing) to handle.When remaining heavy section r1 crosses when thin, abundant inadequately as the function of etching mask, so the thickness of residual heavy section r1 is preferably more than 0.7 μ m.
(G) then, shown in Fig. 1 F, residual heavy section r1 as mask, to carrying out etch processes by removing the metal film 7 ' that above-mentioned thinner wall section r2 exposes, is formed source electrode and drain electrode 7 thus.
Then, shown in Fig. 1 G, as mask, the 2nd amorphous silica film 6 ' that the etch processes of the metal film 7 ' by last time is exposed carries out etch processes with residual heavy section r1, forms the 2nd amorphous silica film 6 after graphical thus.
(H) then, remove heavy section r1.The method of removing of heavy section r1 can adopt well-known gimmicks such as ashing (ashing) processing to carry out.
In operation up to now, can obtain the structure shown in Figure 10 as the aforementioned and the Micropicture of same structure.
Then, can make the liquid crystal array substrate by aforesaid Figure 11～operation shown in Figure 15 and same operation.That is, (I) as shown in figure 11, form the 2nd dielectric film 8 ' on the Micropicture that in the operation of last time, obtains.The 2nd dielectric film 8 ' for example is by SiN xForm.
(J) go up formation photoresist tunicle at the 2nd dielectric film 8 ', make this photoresist tunicle form figure by photoetching process, this photoetching process comprises by mask and the operation that selectivity is exposed, and forms resist pattern R4 (the 3rd photo-mask process) as shown in figure 12.The resist pattern R4 that obtains is carried out etching as mask to the 2nd dielectric film 8 ',, as shown in figure 13, obtain being patterned into the 2nd dielectric film 8 of the shape that is formed with contact hole then by removing resist pattern R4.
(K) as shown in figure 14, on the 2nd dielectric film 8 that forms figure, form nesa coating 9 '.Nesa coating 9 ' is for example formed by ITO (tin indium oxide).
(L) go up formation photoresist tunicle at nesa coating 9 ', make this photoresist tunicle form figure by photoetching process, this photoetching process comprises by mask and the operation that selectivity is exposed, and forms resist pattern R5 (the 4th photo-mask process) as shown in figure 15.
Then, the resist pattern R5 that obtains is carried out etching as mask to nesa coating 9 ', then by removing resist pattern R5, as shown in figure 16, formation has the nesa coating 9 of figure, thereby obtains the liquid crystal array substrate.
Holding liquid crystal between liquid crystal array substrate that obtains as mentioned above and subtend substrate, and adopt well-known method to assemble and can obtain liquid crystal display cells.
According to present embodiment, can form the step resist pattern R of high elching resistant, so after this step resist pattern R is carried out etching as mask to metal film 7 ', the 2nd amorphous silica film 6 ', etching block film 5 ' and the 1st amorphous silica film 4 ' of matrix 10, can carry out etching to metal film 7 ' and the 2nd amorphous silica film 6 ' with the heavy section r1 of this step resist pattern R as mask.
Therefore, can reduce the number of times that in the manufacturing process of liquid crystal array substrate, carries out photo-mask process.For example, in the method shown in Fig. 2～15, need carry out 5 photo-mask processs (the 1st～the 5th photo-mask process) for making the liquid crystal array substrate, and in the present embodiment, can make the liquid crystal array substrate of same structure by carrying out 4 photo-mask processs (the 1st～the 4th photo-mask process).Thus, can control the consumption of photoresist, also can simplify operation, so can cut down the manufacturing cost of liquid crystal array substrate.
In addition, the step resist pattern R that forms in the present embodiment has good thermotolerance and can prevent the distortion that the back baking occurs when handling.By implementing the back baking, can further improve the thermotolerance and the elching resistant of step resist pattern.
Also have, in the present embodiment, the cross section of step resist pattern is recessed shape, and the step resist pattern is because of the difference thickness difference in zone, can be shape, the Micropicture that is formed by etching suitably be designed according to shape with heavy section and thinner wall section.For example, can be that shape is protruded in the cross section that is provided with thinner wall section in the outside of heavy section, also can be mountain, cross section type shape.
In addition, in the present embodiment, apply the present invention to make the operation of α-Si (amorphous silica) shape tft array substrate of structure shown in Figure 16, but be not limited to the liquid crystal array substrate of this structure.The present invention can be used for various manufacturings with liquid crystal array substrate of pixel graphics, uses the formation method of Micropicture of the present invention to form the partial pixel figure, can obtain the effect identical with present embodiment thus.
In following embodiment and comparative example, form the step resist pattern, estimate thermotolerance, anti-dry-etching and moisture-proof formula etching.The evaluation of characteristic is carried out as described below.
(1) thermotolerance evaluation:
For the resist pattern that in embodiment and comparative example, obtains, under 130 ℃, carried out heat treated 300 seconds, be designated as zero with what being out of shape did not appear in the shape of resist pattern, occur being designated as of distortion *.
(2) anti-dry-etching evaluation:
For the resist pattern that in embodiment and comparative example, obtains, use dry-etching device " TCE-7612X " (device name; The chemical industry corporate system is answered in Tokyo), use CF 4, CHF 3, He is as etching gas, be respectively 40 milliliters/min, 40 milliliters/min, 160 milliliters/min, under the reduced atmosphere of 300mTorr ( 39.9Pa), in 700W-400kHz, place (stage) temperature is that 20 ℃, target temperature are under 25 ℃ the treatment conditions, carrying out dry-etching handles, will be out of shape appear in the shape of resist pattern before and after handling be designated as zero, occur being designated as of distortion *.
(3) moisture-proof formula etching is estimated:
For the resist pattern that in embodiment and comparative example, obtains, the substrate that forms this resist pattern is immersed in the Wet-type etching liquid that temperature is set as 20 ℃ [contains hydrofluorite (HF)/ammonium fluoride (NH 4F)=1/6 the aqueous solution 20 quality % of the potpourri of (mass ratio)] in 10 minutes, carry out wet etch process thus, the resist pattern after handling is not designated as zero from the situation that basal substrate is peeled off, situation about peeling off is designated as *.
(embodiment 1)
The modulation positive light anti-etching agent composition.
Prepare (A) composition: the cresols novolac resin [obtains the mixing phenols of metacresol/paracresol=4/6 (mol ratio) and formaldehyde generation condensation reaction by conventional method, the resin of weight-average molecular weight (Mw)=5000] 100 mass parts, (B) composition: [two (2,3,5-trimethyl-4-hydroxyphenyl)-and 2-hydroxyphenyl methane] 10 mass parts, (C) composition: [2,3,4,1 mole of 4 '-tetrahydroxybenzophenone and 1, the esterification reaction product that 2-naphthoquinones two nitrine-5-sulfonic acid chloride are 2.34 moles] 29.7 mass parts, (D) composition: [PGMEA] 430 mass parts, after uniform dissolution above-mentioned (A)～(D) composition, as surfactant, to wherein cooperating BYK-310 (Bikchemi corporate system) 400ppm, use the membrane filter of aperture 0.2 μ m to filter above-mentioned substance, be modulated into positive light anti-etching agent composition.
Use to adopt central authorities to drip and the resist applying device [TR-36000 (chemical industry (strain) system is answered in Tokyo)] of spin-coating method, the positive light anti-etching agent composition that obtains is rotated coating 10 seconds with 1000rpm, and (360mm * 460mm) goes up and forms resist layer at the glass substrate that is formed with the Ti film thus.
Then, the temperature of heating plate is made as 130 ℃, cure by having reserved about 1mm vicinity at interval, carry out 60 seconds the 1st drying, then, the temperature of heating plate is made as 120 ℃, cures by having reserved about 0.5mm vicinity at interval, implement 60 seconds the 2nd drying, form the photoresist tunicle of thickness 2.0 μ m.
This photoresist tunicle is carried out by the exposure of the selectivity of mask, carry out development treatment, cleaning and form figure, use high-pressure mercury-vapor lamp (output wavelength is the light of 200～600nm) enforcement exposure to be 3000mJ/cm then 2UV solidify (irradiation) and handle formation step resist pattern.
The step resist pattern that obtains is the recessed shape in cross section as shown in Figure 1, and the thickness of heavy section is that the thickness of 2.0 μ m, thinner wall section is 0.8 μ m, whole wide be 13 μ m, the wide of thinner wall section is 5 μ m.
About this step resist pattern, the result who estimates its thermotolerance, anti-dry-etching and moisture-proof formula etching is as shown in table 1 below.
(embodiment 2)
Use the positive light anti-etching agent composition identical, adopt the step formation step resist pattern identical with embodiment with embodiment 1.Wherein, the cross section is made in the formation of step resist pattern protrude shape, it is of a size of, and the thickness of heavy section is that the thickness of 2.0 μ m, thinner wall section is 0.8 μ m, whole wide be 13 μ m, the wide of thinner wall section is 5 μ m.
About this step resist pattern, the result who estimates its thermotolerance, anti-dry-etching and moisture-proof formula etching is as shown in table 1 below.
(embodiment 3)
After being identically formed the step resist pattern with embodiment 1, relative therewith, under 130 ℃, carry out the back baking and handled 300 seconds.
Handle step resist pattern afterwards about the back baking, the result who estimates its thermotolerance, anti-dry-etching and moisture-proof formula etching is as shown in table 1 below.
(embodiment 4)
After being identically formed the step resist pattern with embodiment 2, relative therewith, under 130 ℃, carry out the back baking and handled 300 seconds.
Handle step resist pattern afterwards about the back baking, the result who estimates its thermotolerance, anti-dry-etching and moisture-proof formula etching is as shown in table 1 below.
(comparative example 1)
Except do not carry out UV solidify to handle and embodiment 1 similarly form the resist pattern of step.
About this step resist pattern, the result who estimates its thermotolerance, anti-dry-etching and moisture-proof formula etching is as shown in table 1 below.
(comparative example 2)
Except do not carry out UV solidify to handle and embodiment 2 similarly form the resist pattern of step.
About this step resist pattern, the result who estimates its thermotolerance, anti-dry-etching and moisture-proof formula etching is as shown in table 1 below.
(comparative example 3)
For the step resist pattern that in comparative example 1, obtains (solidifying), carry out the back baking in the same manner with the foregoing description 3 and handle without UV.
Handle step resist pattern afterwards about the back baking, the result who estimates its thermotolerance, anti-dry-etching and moisture-proof formula etching is as shown in table 1 below.
(comparative example 4)
For the step resist pattern that in comparative example 2, obtains (solidifying), carry out the back baking in the same manner with the foregoing description 4 and handle without UV.
Handle step resist pattern afterwards about the back baking, the result who estimates its thermotolerance, anti-dry-etching and moisture-proof formula etching is as shown in table 1 below.
Table 1
UV solidifies The back baking Thermotolerance Anti-dry-etching method Moisture-proof formula etching method
Embodiment 1 Have Do not have ○ ○ ×
Embodiment 2 Have Do not have ○ ○ ×
Embodiment 3 Have Have ○ ○ ○
Embodiment 4 Have Have ○ ○ ○
Comparative example 1 Do not have Do not have × × ×
Comparative example 2 Do not have Do not have × × ×
Comparative example 3 Do not have Have - ※ - ※ - ※
Comparative example 4 Do not have Have - ※ - ※ - ※
※: after the back baking is handled, because of distortion appears in resist pattern, so do not estimate thermotolerance, anti-dry-etching and moisture-proof formula etching.

Claims (14)

1, a kind of formation method of resist pattern is characterized in that having:
(A) on matrix, form the photoresist tunicle operation,
(B) graphics shape that above-mentioned photoresist tunicle is patterned into have heavy section and thinner wall section through containing the photo-mask process of selective exposure, form because of the operation of the resist pattern of the different shape of regional different thickness and
(C) carry out above-mentioned graphical after, carry out UV at described resist pattern after graphical whole and solidify and handle and form the operation of step resist pattern with heavy section and thinner wall section.
2, the formation method of resist pattern according to claim 1 is characterized in that having:
(D) after carrying out above-mentioned UV curing processing, carry out the operation that the back baking is handled.
3, resist pattern formation method according to claim 1, it is characterized in that, described matrix is the matrix that has sandwich construction on glass substrate, and described sandwich construction is to have gate electrode, the 1st dielectric film, the 1st amorphous silica film, etching block film, the 2nd amorphous silica film and source-drain electrode to form the sandwich construction of using metal film from glass substrate side lamination successively.
4, resist pattern formation method according to claim 2, it is characterized in that, described matrix is the matrix that has sandwich construction on glass substrate, and described sandwich construction is to have gate electrode, the 1st dielectric film, the 1st amorphous silica film, etching block film, the 2nd amorphous silica film and source-drain electrode to form the sandwich construction of using metal film from glass substrate side lamination successively.
5, a kind of formation method of Micropicture is characterized in that, after the described method of use claim 1 forms described step resist pattern, has following operation:
(E) this step resist pattern is implemented etch processes as mask to above-mentioned matrix; Then
(F) this step resist pattern is carried out ashing treatment, remove above-mentioned thinner wall section;
(G) after removing above-mentioned thinner wall section, heavy section is implemented etch processes as mask to above-mentioned matrix; Then
(H) remove the heavy section of above-mentioned step resist pattern.
6, a kind of formation method of Micropicture is characterized in that, after the described method of use claim 2 forms described step resist pattern, has following operation:
(E) this step resist pattern is implemented etch processes as mask to above-mentioned matrix; Then
(F) this step resist pattern is carried out ashing treatment, remove above-mentioned thinner wall section;
(G) after removing above-mentioned thinner wall section, heavy section is implemented etch processes as mask to above-mentioned matrix; Then
(H) remove the heavy section of above-mentioned step resist pattern.
7, a kind of formation method of Micropicture is characterized in that, after the described method of use claim 3 forms described step resist pattern, has following operation:
(E) this step resist pattern is implemented etch processes as mask to above-mentioned matrix; Then
(F) this step resist pattern is carried out ashing treatment, remove above-mentioned thinner wall section;
(G) after removing above-mentioned thinner wall section, heavy section is implemented etch processes as mask to above-mentioned matrix; Then
(H) remove the heavy section of above-mentioned step resist pattern.
8, a kind of formation method of Micropicture is characterized in that, after the described method of use claim 4 forms described step resist pattern, has following operation:
(E) this step resist pattern is implemented etch processes as mask to above-mentioned matrix; Then
(F) this step resist pattern is carried out ashing treatment, remove above-mentioned thinner wall section;
(G) after removing above-mentioned thinner wall section, heavy section is implemented etch processes as mask to above-mentioned matrix; Then
(H) remove the heavy section of above-mentioned step resist pattern.
9, a kind of formation method of Micropicture is characterized in that, after the described method of use claim 3 forms described step resist pattern, has following operation:
(E ') described step resist pattern is carried out etch processes to above-mentioned source-drain electrode formation with metal film, above-mentioned the 2nd amorphous silica film, above-mentioned etching block film and above-mentioned the 1st amorphous silica film as mask; Then
(F) this step resist pattern is carried out ashing treatment, remove above-mentioned thinner wall section;
(G ') after removing above-mentioned thinner wall section, heavy section is formed with metal film and above-mentioned the 2nd amorphous silica film enforcement etch processes above-mentioned source-drain electrode as mask, stop rete to expose above-mentioned etching; Then
(H) remove the heavy section of above-mentioned step resist pattern.
10, a kind of formation method of Micropicture is characterized in that, after the described method of use claim 4 forms described step resist pattern, has following operation:
(E ') described step resist pattern is carried out etch processes to above-mentioned source-drain electrode formation with metal film, above-mentioned the 2nd amorphous silica film, above-mentioned etching block film and above-mentioned the 1st amorphous silica film as mask; Then
(F) this step resist pattern is carried out ashing treatment, remove above-mentioned thinner wall section;
(G ') after removing above-mentioned thinner wall section, heavy section is formed with metal film and above-mentioned the 2nd amorphous silica film enforcement etch processes above-mentioned source-drain electrode as mask, stop rete to expose above-mentioned etching; Then
(H) remove the heavy section of above-mentioned step resist pattern.
11, the formation method of Micropicture according to claim 9, it is characterized in that, the etch processes that above-mentioned source-drain electrode forms with metal film is that wet etch process or dry-etching are handled, and the etch processes of above-mentioned the 2nd amorphous silica film is that dry-etching is handled.
12, the formation method of Micropicture according to claim 10, it is characterized in that, the etch processes that above-mentioned source-drain electrode forms with metal film is that wet etch process or dry-etching are handled, and the etch processes of above-mentioned the 2nd amorphous silica film is that dry-etching is handled.
13, a kind of manufacture method of liquid crystal display cells has the operation that forms pixel graphics and make the liquid crystal array substrate on glass substrate, it is characterized in that,
The part of above-mentioned pixel graphics is that the formation method by any described Micropicture in the claim 5～8 forms.
14, a kind of manufacture method of liquid crystal display cells is characterized in that, after by any described method formation Micropicture in the claim 9～12, has:
(I) on this Micropicture, be provided with the 2nd dielectric film operation,
(J) by photoetching to the 2nd dielectric film carry out patterned operation,
(K) form on the 2nd dielectric film after graphical nesa coating operation,
(L) by photoetching nesa coating is carried out patterned operation.
CNB2004101003126A 2003-12-12 2004-12-09 Erosion resistant pattern forming method, micro-pattern forming method using the same Expired - Fee Related CN100340925C (en)

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JP4611690B2 (en) * 2004-09-03 2011-01-12 東京応化工業株式会社 Method for forming resist pattern, method for forming fine pattern using the same, and method for manufacturing liquid crystal display element
KR101522240B1 (en) * 2007-12-24 2015-05-22 엘지디스플레이 주식회사 Liquid crystal display device and method of fabricating the same
KR101375855B1 (en) 2008-11-27 2014-03-18 엘지디스플레이 주식회사 Method of fabricating oxide thin film transistor
CN104253037A (en) * 2013-06-30 2014-12-31 无锡华润上华半导体有限公司 Method for alleviating burning of photoresist during etching
CN106505033B (en) * 2016-11-16 2019-06-25 深圳市华星光电技术有限公司 Array substrate and preparation method thereof, display device
CN107195540B (en) * 2017-06-05 2021-01-26 京东方科技集团股份有限公司 Manufacturing method of array substrate, array substrate and display device

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