TWI263118B - Positive photoresist composition and method for forming resist pattern - Google Patents

Abstract

A positive photoresist composition is provided which can prevent deformation of a resist pattern in high temperature postbaking steps, and decrease degassing in high temperature heating. This positive photoresist composition includes (A) alkaline soluble novolak resin having polystyrene reduced weight average molecular weight of not less than 20000, and containing not more than 4% of binuclear compounds, (B) a compound containing a phenolic hydroxyl group with Mw of no more than 1000, (C) naphthoquinonediazido group containing compound, and (D) an organic solvent.

Description

1263118 (1) Field of the Invention The present invention relates to the formation of a positive-type photoresist composition and a photoresist pattern. [Prior Art] Manufacturing of a liquid crystal display element using a glass substrate hitherto In the field, since it is relatively inexpensive and can form a resist pattern with excellent sensitivity, resolution, and shape, it is often used as a basic soluble resin using a phenolic enamel resin, and a compound containing a naphthoquinonediazide group is used. A positive-type photoresist composition as a photosensitive component has been reported as a photoresist material (Patent Documents 1 and 2 below). [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-75272 (Patent Document 2) discloses a liquid crystal panel for a liquid crystal display device, for example, used on an optical substrate to form an amorphous crucible. A panel of a thin film transistor is constructed 'but in recent years, polycrystalline germanium has been favored instead of amorphous germanium. The low-temperature polycrystalline silicon formed in the low-temperature step of 60 ° C or lower is smaller than the amorphous germanium and has high mobility, so it is focused on the second-generation high-performance liquid crystal substrate. However, on a TFT formed of a low-temperature polysilicon, a polycrystalline germanium film is formed on a glass substrate in a low temperature step, and P and B are introduced into the low-temperature polycrystalline film. In the so-called "implantation step", it is necessary to enter a very high level. Impurity of concentration (2) 1263118 This implantation step is carried out on a low-temperature polycrystalline germanium glass substrate on which a low-temperature polycrystalline germanium film is formed on a glass substrate, and is formed under the condition of high degree of vacuum under the condition of forming a photoresist pattern. The heat generation of the impurities causes the photoresist pattern on the substrate to be heated, which causes a certain component in the photoresist pattern to vaporize and has a problem of reducing the degree of vacuum in the processing chamber.

Thus, the means for solving this problem is known to be an effective means of adding a so-called "post-baking" heat treatment step before the implantation step. Thereafter, the baking is performed under a temperature condition close to the heating temperature at the time of implantation, for example, at a high temperature of 200 ° C or higher, and the photoresist pattern is preheated to reduce the pattern from the photoresist pattern at the implantation step. The amount of outgassing is for its purpose. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention]

However, when the photoresist composition for manufacturing a liquid crystal display element is post-baked, the photoresist pattern flows and has a problem that shape change is liable to occur. Moreover, in the post-baking, the micropores and cracks which are polluted in the treatment chamber and which are porous in the photoresist pattern are caused by the amount of degassing from the photoresist pattern, and also have a shrinkage phenomenon in which the volume of the photoresist pattern is reduced. problem. In view of the foregoing, the present invention provides a photoresist composition capable of preventing deformation of a resist pattern during a high-temperature post-baking step, and capable of reducing a degassing amount at a high-temperature heating, and a method of forming a photoresist pattern using the composition. For its purpose. [Means for Solving the Problems] The inventors of the present invention have made efforts to solve the above problems, and as a result, -6 - (3) 1263118 has been used, and the mass average molecular weight converted into polystyrene is used up to 20,000 or more. When the phenolic enamel resin having a dinuclear body content of as little as 4% or less is used as an alkali-soluble resin, the heat resistance of the photoresist pattern can be improved, and the amount of degassing can be reduced, and the present invention can be completed. That is, the positive-type resist composition of the present invention is characterized in that (A) the mass average molecular weight (Mw) converted to polystyrene by gel permeation chromatography is 20,000 or more and the dinuclear content is 4% or less. An alkali-soluble novolac resin, (B) a compound having a phenolic hydroxyl group having a molecular weight of i 〇〇〇 or less, (C) a compound containing a naphthoquinonediazide group, and (D) an organic solvent. The positive resist composition of the present invention can be suitably used as a resist pattern material for producing a liquid crystal display element. Accordingly, the present invention also provides a liquid crystal display element produced using the foregoing positive photoresist composition. Moreover, the present invention provides a step of subjecting the positive resist composition of the present invention to a substrate and then post-baking to form a photoresist film, and the step of selectively exposing the photoresist film to the foregoing a photoresist pattern formed by selectively irradiating a photoresist film using an alkaline aqueous solution to form a photoresist pattern on the substrate, wherein the substrate has a low temperature polycrystalline germanium film on the glass substrate A polycrystalline germanium glass substrate is a photoresist pattern forming method characterized by the same. Further, for the photoresist pattern after the development processing, high temperature post-baking of 200 ° C or higher can be performed. The "constituting unit" as used in the present specification means a unit unit constituting a polymer (resin). -7- (5) 1263118 The coating property of the sheet tends to be deteriorated. Therefore, the upper limit M of the M w of the component (A) is preferably about 50,000. A more preferable range of Mw of the component (A) is about 21,000 to 35,000. Further, when the content of the dinuclear body in the component (A) is 4% or less, the degassing amount at the time of high-temperature heat treatment is preferably 200 ° C or higher, preferably 220 to 250 1: in the post-baking, Moreover, the occurrence of shrinkage of the photoresist pattern, micropores, cracks, and the like can be prevented, and contamination in the processing chamber caused by degassing of the photoresist pattern can be suppressed. The smaller the content of the dinuclear material in the component (A), the lower the amount of degassing during heating, but the smaller the content of the dinuclear body, the higher the manufacturing cost, so the lower limit of the dinuclear content in the component (A) is About 0.1% is better. The dinuclear content in the component (A) is more preferably in the range of about 1.0 to 3.0%. Specific examples of the alkali-soluble novolac resin (A) include a phenolic enamel resin obtained by reacting the phenols exemplified below with an aldehyde 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, and 3,5-dimethyl a xylenol such as phenol or 3,4-xylenol; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5 -triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl- Alkylphenols such as 5-methylphenol; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, m-propyl Alkoxyphenols such as oxyphenol; o-isopropenylphenol, p-isopropenylphenol, 2-methyl-9-(6) 1263118--4-isopropenylphenol, 2-ethyl-4 - isopropyl phenol such as isopropenyl phenol; aryl phenols such as phenylphenol; 4,4 dihydroxybiphenyl, binocular A, resorcinol, hydroquinone, pyrogallol, etc. Polyhydroxyphenols and the like. They 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 preferred. The aldehydes may, for example, be formaldehyde, paraformaldehyde, trioxane, acetonide, propionaldehyde 'butyraldehyde, trimethyl acetaldehyde, acrolein, crotonaldehyde, cyclohexanal, decanoic acid, decyl propyl aldehyde. , benzaldehyde, acetal, phenyl bromide, α-phenylpropanal,/5-phenylpropanal, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methyl Benzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamaldehyde, and the like. They may be used alone or in combination of two or more. Among these aldehydes, formaldehyde is preferred in terms of ease of availability, and in particular, in order to improve heat resistance, it is preferred to use hydroxybenzaldehyde and formaldehyde in combination. As the acid catalyst, hydrochloric acid, sulfuric acid, formic acid, oxalic acid, p-toluenesulfonic acid or the like can be used. The Mw and the dinuclear content of the (Α) component are synthesized by a synthesis reaction of a usual phenolic enamel resin, and a condensate of a phenol and an aldehyde is synthesized, and then the low molecular region can be cut out according to a known classification or the like. Adjustment. The treatment such as classification is, for example, a phenolic lacquer resin obtained by a condensation reaction in a good solvent, for example, an alcohol such as methanol or ethanol, a ketone such as acetone or methyl ethyl ketone, and ethylene glycol monoethyl ether acetate or tetrahydrofuran. The method of dissolving in the middle, and then injecting it into the water to precipitate it can be carried out. Further, in the case of the synthesis reaction (condensation reaction) of the phenolic enamel resin, -10-(7) 1263118 The content of the dinuclear body can also be reduced by steam distillation (JP-A-2000-0123). Further, in the present invention, the component (A) may be composed of a phenolic enamel resin, and may be composed of two or more phenol awakening varnish resins. When it is composed of two or more kinds of phenolic enamel resins, it may contain a phenolic enamel resin having a Mw of 20 000 or more and a dinuclear content of not more than 4%, and the (A) component is M w 2 0 0 as a whole. 0 0 or more 'dinuclear body content of 4% or less can be. Therefore, the M w and the dinuclear content of the component (A) can be adjusted by appropriately mixing two or more kinds of phenolic enamel resins having different M w and dinuclear contents. [(Α1) component] In the present invention, the phenol styrofoam resin (A 1 ) having an M w of 30,000 to 4,000 is preferably contained in the alkali-soluble phenol resin (A ). If the M w of the component (A 1 ) is less than 3,000, it is difficult to prepare a photoresist composition excellent in heat resistance, and if it exceeds 40,000, it is difficult to be on the substrate in the stripping step of the photoresist pattern. The tendency to strip the photoresist pattern is such that the preferred range of Mw which is not good ((1) is 32000 to 38000. The component (A 1 ) is preferably a constituent unit derived from m-cresol and a constituent unit derived from 2,3,5-trimethylphenol. The constituent unit derived from m-cresol contributes to an improvement in sensitivity, but in the resolution, film thinning tends to occur. On the other hand, the constituent unit derived from 2,3,5-trimethylphenol has a tendency to lower the sensitivity, and 2,3,5-trimethylphenol is more expensive, but contributes to the resolution. Pick up. _ -11 - (8) 1263118 Both cresol and 2,3,5-trimethylphenol are highly reactive, and it is difficult to form a dinuclear. In particular, the reactivity of m-cresol is high. The phenolphthalein Mw obtained by the reaction of m-cresol and 2,3,5-trimethylphenol is a component (1) of up to 30,000 to 40,000, and can suppress deterioration of photoresist sensitivity and resolution and improve heat resistance. good. The content of the dinuclear compound in the component (A1) is preferably 4.0% or less. The smaller the content of the dinuclear body in the fraction, the smaller the dinuclear content is, the larger the dinuclear content is, so the lower limit 値 is about 0.1%. good. The (A 1 ) dinuclear content is more preferably in the range of about 1.0 to 3.0%. The constituent unit derived from the meta-toluene S component of the (A 1 ) component derived from the phenolic constituents is a constituent unit derived from 2,3,5-trimethylphenol containing 80 mol%. It contains 5 moles. In particular, the (A 1 ) component is a phenolic enamel resin composed of m-cresol derived from a constituent unit derived from 2,3,5-trimethylphenol, and has heat resistance to a resist pattern, and light. It is preferable that the resist pattern removability in the resisting step is good. In this case, the molar ratio of the constituent unit derived from the E phenol/derived from 2,3,5-trimethylphenol is preferably in the range of 80/20 to 95/5. When the component (A1) is used, the content of (A1) in the component (A) is preferably 50% by mass or more, more preferably 70% by mass or more and 100% by mass. If the component (A 1 ) is less than the above range, it is difficult to form an excellent photoresist pattern. The method for synthesizing the phenolic enamel resin (A 1 ) can be quantified by the usual sub-quantization and, therefore, the lacquer resin, the (A 1 ) component of the composition is in the unit of the manufacturing cost component, and the component is composed of The composition of the component type is compared with the composition of the white component-toluene. It can also be used for the synthesis of heat-resistant phenolic hydrazine-12- (9) 1263118 lacquer resin, using phenols containing at least m-cresol and 2,3,5-trimethylphenol, with formaldehyde and according to the usual method. The condensate is synthesized, and thereafter, the Mw and the dinuclear content can be adjusted to a desired range by operation such as classification. [(A 2 ) component] Further, the component (A) is a mixture of two or more types of phenolic enamel resin, and the phenolic enamel resin (A2) having a Mw of 3000 to 7,000 is preferably the component (A2). If the Mw is less than 3,000, it is difficult to prepare a photoresist composition excellent in heat resistance, and if it exceeds 7,000, the sensitivity of the photoresist tends to be lowered, which is not preferable. The component (A2) is preferably a constituent unit derived from m-cresol and a constituent unit derived from p-cresol. As described above, the constituent unit derived from m-cresol contributes to the improvement of the sensitivity, but in the resolution, the film tends to be thinned. On the other hand, although the constituent unit derived from p-cresol tends to lower the sensitivity, it contributes to the improvement of the resolution. Further, 'p-cresol is inexpensive', but when compared with m-cresol and 2,3,5-trimethylphenol, the reactivity is low. Therefore, by including the component (A 2 ) in the component (A), the photoresist, the sensitivity, the resolution, and the residual film ratio of the composition can be effectively improved. The dinuclear content in the component (A2) is preferably 10% or less. (A2) The smaller the content of the dinuclear component in the component, the better. However, if the content of the dinuclear body is too small, the manufacturing cost is increased, so the lower limit is preferably about 1%. The content of the nucleus of -13-(10) 1263118 in the component (A2) is more preferably about 3.0 to 7.0%. (Α2) In the total constituent unit derived from the phenols constituting the phenol, the constituent unit derived from m-cresol is 30% by mole or more, and the constituent % derived from p-toluene is It is preferably more than 60% by mole. In particular, the (A 2 ) component is a two-component phenolic enamel resin composed of a constituent unit derived from m-toluene and a constituent unit derived from p-cresol, and a photoresist pattern having an excellent residual film ratio can be formed. The words are better. In this case, the constituent unit derived from m-cresol/the molar ratio of the constituent unit derived from p-cresol is preferably 30 / 70 to 40 / 60. By including the component (A2) in the component (A), good sensitivity and resolution can be easily achieved. When the component (A2) is used, the content of the component (A2) in the component (a) is preferably from 5 to 70% by mass, more preferably from 10 to 60% by mass. When the amount of the component (A2) is less than the above range, the effect of improving the sensitivity and the residual film ratio is insufficient, and if it is too large, the heat resistance tends to be deteriorated. The method for synthesizing the phenolic enamel resin (A2) can be carried out by using a synthesis reaction of a usual phenolic enamel resin, using a phenol having at least m-cresol and p-cresol, synthesizing a condensate with formaldehyde and according to a conventional method, and thereafter By operation such as classification, the Mw and the dinuclear content can be adjusted to a desired range. In the present invention, the component (A) contains both the component (A1) and the component (A2), and the total amount of Mw is 20,000 or more, and the dinuclear content is preferably 4% or less. The grading treatment may be applied as needed, and the Mw and the dinuclear body content may be adjusted. In this case, the content ratio of the (A1) component to the (A2) component is preferably in the range of (A1) / (A2) = 1/1 to 5/1 (mass ratio), and is 1.5/1 to 3/1 ( Quality ratio) is better. -14- (11) 1263118 Further, the phenolic enamel resin other than (A1) or (A2) may be contained in the component (A) as desired. The total content of (A1) and (A2) in the component (A) is preferably 50% by mass or more and more preferably 90% by mass. It can also be 100% by mass. [(B) ingredient]

The positive resist composition of the present invention has an effect of improving sensitivity by containing a compound (B)' having a phenolic hydroxyl group having a molecular weight of 1 Å or less. In particular, in the field of manufacturing liquid crystal display elements, 'increasing the throughput is a very large problem, and since the amount of photoresist consumed is large, it is desirable that the photoresist composition is highly sensitive and inexpensive, and if the component (B) is used, It is better to achieve high sensitivity at a lower cost. Further, when the component (B) is contained, the surface insoluble layer is strongly formed in the photoresist pattern. Therefore, the film thickness of the photoresist film which is not exposed at the time of development is small, and the occurrence of the difference in development time can be suppressed. The image is uneven, so it is better.

When the molecular weight of the component (B) exceeds 1 Å, the effect of improving the sensitivity is not obtained, which is not preferable. In the component (B), a phenolic hydroxyl group-containing compound having a molecular weight of 1,000 or less used in the positive resist composition for producing a liquid crystal display element can be suitably used, but the phenolic hydroxyl group is represented by the following general formula (ΠΙ). The compound is effective in improving the sensitivity and is also excellent in heat resistance. -15- (12) 1263118

In the formula, R| to R8 are each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a ring-shaped base having 3 to 6 carbon atoms. ; R9 to R11 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; q is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a residue represented by the following chemical formula ();

(wherein R12 and R13 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms; c is an integer representing 1 to 3); a, b are integers representing 1 to 3; d is an integer representing 0 to 3, or Q is a bond with R9 and carbon atoms between R9 and Q and R9 together form carbon The chain 3 to 6 cycloalkyl groups; η is an integer representing 0 to 3] Any one of them may be used, or two or more of them may be used. In the compound containing a phenolic hydroxyl group, a compound represented by the following formula (I) (h[l-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)) Ethyl]benzene) and bis(2.3,5-trimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane are excellent in high sensitivity and high residual film rate, so they are particularly excellent, and The compound of the above formula (I)-16-(13) 1263118 is preferably excellent in terms of high sensitivity.

OH

C ——CH3 (i)

The amount of the component (B) is preferably from 1 to 25 parts by mass, preferably from 5 to 20% by mass, based on 100 parts by mass of the alkali-soluble novolac lacquer resin of the component (A). When the content of the component (B) in the resist composition is too small, the effect of improving the high sensitivity and the high residual film ratio cannot be sufficiently obtained. If the content is too large, the residue on the surface of the substrate after development is likely to occur, and the raw material costs. It is also high, so it is not good. C) Component] (C) The compound containing a nitrogen group in the invention is a photosensitive component. For the δ hai (C) component, for example, a positive resistive composition for manufacturing a liquid crystal display element can be used as a photosensitive component. For example, the component (c) is preferably a acetation reaction product (c 1 ) and/or a phenolic hydroxyl group-containing compound represented by the following formula (π) and a 1,2-naphthoquinonediazidesulfonic acid compound. Or an esterification reaction product of the compound containing a trans group represented by the following formula (111) with a 1,2-naphtho-azidosulfonic acid compound, -17-(14) 1263118 (C 2 ). The above 1, 2 - Cai 醌 diazido sulfonic acid compound quinonediazide-5-sulfonate compound. (0H) [wherein, R1 to R8 each independently represent a hydrogen atom, a halogen atom, a hospital group, an alkoxy group having 1 to 6 carbon atoms, or a carbon number of 3 to 6 f|; and R9 to R11 are each independently represented. a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a group having 1 to 6 carbon atoms, or the following chemical formula (iv), preferably 1,2-naphthyl

_b art) carbon number 1 to 6 leaving a cycloalkyl group; Q is a hydrogen residue

(wherein R and R1/ each independently represent a hydrogen atom, an alkyl group of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or an integer of 1 to 3 of a carbon number of 3 to 6), or R9 combines and R9, and (^ and R9 together form a carbon chain of 3 to 6 cycloalkyl groups; a, b are 1 to 3, carbon number 1 to 6 yards; c is a carbon atom between the tables Integer; d is an integer of Table -18-(15) 1263118 〇 3 3; n is an integer representing 0 to 3] The average esterification ratio of the component (C1 ) is 50 to 70%, preferably 55 to 65%. When the film is less than 50%, film thinning is likely to occur, and the residual film rate is not good. If it exceeds 70%, the storage stability tends to be lowered, so it is not good. The average esterification rate of the component (C2) is 40 to 60%, preferably 45 to 55%. When the film is less than 40%, film thinning is likely to occur after development, and the residual film ratio is liable to become low. %, the sensitivity is remarkably deteriorated. The (C 2 ) component is an esterification reaction product of a phenolic hydroxyl group-containing compound represented by the following formula (V) and a 1,2-naphthoquinonediazidesulfonic acid compound ( C3), especially due to the high resolution of the photoresist pattern formation Therefore, preferably

(V) Further, in addition to the above-mentioned photosensitive component, the component (c) may be used in another component of the component (c) in an amount of 30% by mass or less, particularly 25% by mass. The following is better. The compounding amount of the component (c) in the photoresist composition of the present invention is a total of p< -19-(16) 1263118 (B ) relative to the phenolic phenol resin (A) and the phenolic hydroxyl group-containing compound. The amount is 100 parts by mass, preferably 15 to 4 parts by mass, more preferably in the range of parts by mass. If the content of the component (C) is less than 'there is a decrease in the transferability, the desired shape cannot be formed. On the other hand, if the content is more than the above range, the sensitivity and resolution of the image are likely to occur after the image is processed. Things. The component (C) is particularly preferable because (c 1 ) is a very inexpensive and highly viscous photoresist composition and is excellent in heat resistance. Further, the component (C) can be selected according to the exposure used in the developing step. For example, when the ghi ray (g ray, h ray, and i ray) is exposed in the step of performing selective exposure, (when used, i-ray exposure may be used, and (C2) components (C1) and (C2) may be preferably used. In particular, in the case of performing i-ray exposure, in the case of using (C 1 ), the mixing ratio thereof is preferably 80 parts by mass or less with respect to (C2) 50 mass%. If the amount of (C1) is too large, the resolution and sensitivity decrease. [(D) component] The composition of the present invention is preferably used as the organic solvent used in the present invention by using the components (A) to (C) and various solutions dissolved in the organic solvent (D) as propylene glycol monomethyl ether (PGMEA). It is excellent in coating properties and is excellent in film thickness uniformity on a large glass substrate. PGMEA is preferably used in a single solvent, but it is preferably in the range of 2 0 to 3 0 ‘the above range i resistance pattern. :, and the modulation of high-sensitivity wavelength, in the case of C1) is appropriate, or the use of (C2) parts (C 1 ,, then the addition of the component 〇 acetate (: photoresist film can be combined with -20 - (17) 1263118 The use of p G 丨 glutinous agent other than EA' may be, for example, lactic acid ethyl acetate, T-butyrolactone, propylene glycol monobutyl ether, etc. When using lactic acid ethyl vinegar, the ratio of the desired mass ratio to PGMEA is 0. The amount of 〜1 to 〇 is preferably in the range of 1 to 5 times. When r-butyrolactone is used, the mass ratio of PGME A is preferably 0.01 to 1 times, preferably 〇. 5~〇. The range of 5 times. Especially in the field of manufacturing liquid crystal display elements, it is usually necessary to form a photoresist film of 0.5 to 2.5 μm on the glass substrate, particularly 1 · 0 to 2 · Ο μ m film thickness Therefore, the use of the organic solvent is such that the total amount of the above components (A) to (C) in the photoresist composition is 30% by mass or less, preferably 15 to 30% by mass based on the total mass of the composition. %, more preferably adjusted to 20 to 28% by mass, is preferable in terms of obtaining good coating properties. [Other components] In the present invention In the composition, various additives such as a surfactant and a storage stabilizer can be used without impairing the object of the present invention. For example, an ultraviolet absorber for preventing halation can be suitably contained, for example, 2, 2\ 4 hydroxybenzophenone, 4-dimethylamino-2',4'-dihydroxybenzophenone, 5-amino-3-methyl-p-phenyl-4-(4-hydroxyphenylazo)pyridinium Azole '4-dimethylamino-4, _ benzylazobenzene, 4-diethylamino-4'-ethoxy azobenzene, 4-diethylaminoazobenzene, curcumin, etc., and Surfactants used to prevent streaks, such as Fuloride FC-430, FC431 (trade name, Sumitomo 3M (share)), Efutop EF122A, EF122B, EF122C, EF126 (trade name, T 〇kem P 1 〇ducts (share) system) Temple 糸 surfactant, -21 - (18) 1263118

Fluorine-sand surfactant such as Megafac R40 (trade name, manufactured by Dainippon Ink and Chemicals Co., Ltd.). In the white, the photoresist composition of the components (A) to (D) has good heat resistance, and the content of the dinuclear body is also suppressed to be small, so that the amount of degassing at the time of high-temperature heating is small. Therefore, it is suitable for use in the formation of the photoresist pattern 5 used in the manufacturing process of the liquid crystal display element accompanying high-temperature post-baking, and is also suitable for use in the manufacture of L C D using a low-temperature polycrystalline solar glass substrate. An embodiment of a method of forming a photoresist pattern of the present invention will be described. First, the positive-type photoresist composition of the present invention prepared in a solution form is applied onto a substrate by a suitable coating means such as a spin coater to form a coating film. The substrate used at this time is a low-temperature polycrystalline germanium glass substrate on which a low-temperature polycrystalline germanium film is formed on a glass substrate. On the low temperature polycrystalline sand glass substrate, a layer other than the low temperature polycrystalline germanium film may be formed as needed. Next, the substrate on which the coating film is formed is dried by heating (prebaking) at about 100 to 140 ° C to form a photoresist film. Next, for the photoresist film, selective exposure is performed through the desired mask pattern. The wavelength at the time of exposure can be suitably used as g ir rays or i rays, and various appropriate light sources can be used. Next, the development of the photoresist after selective exposure is carried out by using a developing solution composed of an alkaline aqueous solution, for example, a 1 to 10% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). For the method of contacting the photoresist film with the developing liquid, for example, a method of filling the liquid from one end to the other end of the substrate, and a nozzle for developing the liquid droplets disposed above the center of the substrate to make the surface of the substrate The whole method of the liquid -22-(19) 1263118. The rear surface is placed for about 50 to 60 seconds and developed to form a resist pattern on the substrate. Thereafter, the developing liquid remaining on the surface of the resist pattern is washed with a washing liquid such as pure water to carry out a washing step. The substrate is a low-temperature polycrystalline germanium glass substrate, and the substrate is supplied to the step of implanting, and after the high-temperature post-baking at 200 ° C or higher for the photoresist pattern after the development process, the implantation step is performed. The heat treatment temperature at the time of the high-temperature post-baking is preferably 220 ° C or higher, and may be, for example, 220 to 250 ° C. According to the method for forming such a resist pattern, the heat resistance of the photoresist composition is good, and the amount of outgas can be suppressed to be reduced. Therefore, even if a high-temperature heat treatment is applied, the flow of the photoresist pattern can be prevented. Discomfort caused by degassing in the treatment room, micropores, cracks, shrinkage, etc. of the photoresist pattern. The formation method of such a photoresist pattern is a formation of a photoresist pattern suitable for use in a manufacturing step of a liquid crystal display element which is accompanied by high-temperature post-baking, and is also suitable for use in the manufacture of an LCD using a low-temperature polycrystalline germanium glass substrate. [Embodiment] [Examples] The physical properties of the positive resist composition were determined by the following treatment. (1) Sensitivity evaluation: The sample (positive photoresist composition) was coated on a glass substrate (3 60 X 4 70 mm 2 ) on which a Cr film had been formed using a spin coater, and the temperature of the hot plate was 13 ° ° C. And the first drying of 60 seconds was carried out with Proximity bake -23- (20) 1263118 at intervals of about 1 mm, and then the hot plate temperature was 1 2 0 ° C and separated by 0 J mm. The next drying of the adjacent baking was performed for 60 seconds to form a photoresist film having a film thickness of 1.5 μm. Next, through the Testchart Mask (Leticul) for reproducing the reticle pattern of the 3.0 μηι line/space photoresist pattern, and using the specular projection analyzer MPA-600 FA (manufactured by Canon Inc.; ghi ray exposure apparatus) Exposure was carried out, followed by contact with an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide (TMAH) at 23 ° C for 60 seconds, and washing with water for 30 seconds, followed by spin drying. The sensitivity was evaluated by the exposure amount (Εορ exposure amount) at the time of reproduction of a resist pattern of 3.0 μm line/space on a substrate. (2) Heat resistance evaluation: The photoresist pattern was formed using the sample (photoresist composition) in the same manner as in the above (1) sensitivity evaluation method. Thereafter, the substrate on which the photoresist pattern was formed was placed on a hot plate heated to 2,300 t. The substrate was heated for 5 minutes. Thereafter, the cross-sectional shape of the photoresist pattern was observed by SEM (Scanning Electron Microscope) photograph. The rate of change of the bottom dimension of the resist pattern is 3.0% or less, which is represented by ◎; when it exceeds 3.0%, 5.0% or less, it is represented by Δ, and when it exceeds 5.0% '10.0% or less, it is represented by △, and when it exceeds 10.0%, it is X. Said. (3) Evaluation of degassing property: -24- (21) 1263118 In the above (2) heat resistance evaluation, the substrate on which the photoresist pattern was formed was heat-treated for 5 minutes, and then, as shown in Fig. 1, above the substrate 1, The degassing components which occurred were collected in a bubbler 3, dissolved in a solvent (THF) 2, and the amount of outgassing was measured by GPC^-analysis, and compared. As a result, almost no degassing component was indicated by 〇, a slight observer was indicated by Δ, and a large number of observers were represented by X (Examples 1 to 5), (Comparative Examples 1 to 3) Examples and Comparative Examples In order to prepare the photoresist composition shown in the following Table 1, the sensitivity evaluation, the heat resistance evaluation, and the degassing property evaluation were performed. The evaluation results are not shown in Table 2 below. The components (A) are (ai) and (a2) below. The compounding weight of the component (A) is 100 parts by mass. In Table 1, (al) / (a2) is a mixture of (a 1 ) and (a2), and the mixture ratio (mass ratio) is shown below. Further, the component (A) is obtained by mixing the following (al) component and the component (a2) in the mixing ratios shown in Table 1, and then subjecting them to a classification treatment to adjust the Mw and the dinuclear content. The Mw, the amount of the dimer (dinucleotide content) described in Table 1 is the number 値. (a 1 ): adding oxalic acid and a concentration of 37% by mass of formaldehyde in a mixture of 90% by mole of m-cresol and 1%, 3,5-trimethylphenol 1 〇mol% and performing according to the usual method The Mw3 00 00 cresol novolac resin obtained by the condensation reaction is subjected to a classification treatment to obtain Mw = 3 5 000, and the phenolic dinuclear content is about 4.0% of cresol novolac lacquer resin (product name: TO_ 5 4 7) , Sumitomo Becklite company). (a2) ················ The cresol novolac lacquer resin having a mass average molecular weight (Mw) of 4000 obtained by the condensation reaction is subjected to a classification treatment to obtain M w = 4500 〇, and the phenolic dinuclear content is about 6% of cresol novolac lacquer resin. (Product name: GTR - Μ 2: manufactured by Qun Rong Chemical Co., Ltd.). The (Β) component is the following (b 1 ) 1 〇 by mass. (b 1 ): a phenolic hydroxyl group-containing compound represented by the above formula (I) (molecular weight 4 2 4 ). The component (C) is the following (C1) or (C3) 27.5 parts by mass of hydrazine (c 1 ): the phenolic hydroxyl group-containing compound 1 represented by the above formula (11) and 1,2-naphthoquinone Azide-5-sulfonyl chloride 2.34 moles of esterification reaction product (average esterification rate of 5 8 · 5 %). (c 3 ): esterification reaction product of the phenolic hydroxyl group-containing compound 1 and the 1,2-naphthoquinonediazide-5-sulfonyl chloride 2·1 1 mole represented by the above formula (V) (Average esterification rate is 53%). The component (D) (organic solvent) is a mass fraction of (d 1 ) 4 1 2 described below. (dl) ·· PGMEA. After the above components (A) to (D) were uniformly dissolved, 'Me gafac R-60 (product name, manufactured by Dainippon Ink and Chemicals Co., Ltd.), which is a surfactant, was added to 400 ppm, and an aperture 〇·2 was used. The membrane filter of μ m is filtered to prepare a positive photoresist composition. -26- (23) 1263118 [Table 1] (A) component (mixing ratio) (M w) (dimer amount) (c) component (combination amount) a 1 / a 2 c 1 Example 1 (1/1 (20000) (4.0%) al /a2 Cl Example 2 (1/1) (22400) (2.5 %) al /a2 cl Example 3 (1.5/1) (24800) (1.5%) a 1 / a2 c 1 / c 3 Example 4 (2/1) (30000) (2.5 % ) (2/1) a 1 /a2 c 1 / c 3 Example 5 (1/1) (22400) (2.5 % (2/1) a 1 / a 2 cl Comparative Example 1 (1/5) (10500) (4.0 %) al /a2 cl Comparative Example 2 (1.2/1) (21500) (5.0 % ) a 1 / a 2 c 1 / c 3 Comparative Example 3 (1 . 2 /1 ) (21500) (5.0 %) (2/1)

-27- (24) 1263118 L « Two J Sensitivity Evaluation (msec) Heat Resistance 1 Example 1 130 (Example 2 1 90 Example 3 280 J Example 4 6 〇〇 (-___ - Example 5 400 L Comparative Example 1 80 Comparative Example 2 100 Comparative Example 3 320 Evaluation of Degassing Property Evaluation Δ 〇〇〇〇 Δ Δ [Effect of the Invention] According to the present invention as described above, it is possible to obtain light capable of preventing the high temperature post-baking step The photoresist composition and the photoresist pattern which can reduce the amount of degassing during high-temperature heating. [Simplified Schematic] [Fig. 1] In Examples 1 to 5 and Comparative Examples 1 to 3, A device for recovering degassing components generated by photoresist pattern heat treatment for evaluating the heat resistance of the positive-type photoresist composition. Main component comparison table 1 substrate -28- 1263118 (25) 2 dissolved J 3 foaming Device

Claims (1)

(1) 1263118 U Pickup, Patent Application No. 93 1 0307 Patent Application No. 1 Revision of the Chinese Patent Application No. 1 of June 1st, 1994. 1. A positive resist composition characterized by An alkali-soluble phenolic enamel lacquer resin (A ) in which the mass average molecular weight (Mw) of the polystyrene is 200 Å or more and the dinuclear content is 4% or less is converted by the gel permeation chromatography with respect to the alkali 100 parts by mass of the phenolic hydroxyl group-containing compound (B) having a molecular weight of 100 Å or less, and 1 to 2 parts by mass of the soluble phenolphthalein lacquer resin (A), relative to the alkali-soluble phenolic enamel resin (A) and containing The total amount of the phenolic hydroxyl group-containing compound (B) is 100 parts by mass, which is 15 to 40 parts by mass of the compound (C) containing a naphthoquinonediazide group, and the total amount of the components (A) to (C), relative to The total mass of the composition is such that the organic solvent has a (D) content of 30 parts by mass or less. 2. The positive resist composition according to claim 1, wherein the component (A) is a phenolic enamel resin (A1) having a mass average molecular weight (Mw) converted to polystyrene of from 30,000 to 40,000. . 3. The positive-type resist composition according to claim 1, wherein the component (A) is a phenolic enamel resin containing a mass average molecular weight (Mw) converted to polystyrene of from 30,000 to 7,000. 4. The positive-type photoresist composition of claim 1 wherein the component (A) is a phenolic enamel resin (A) containing a mass average molecular weight (Mw) converted to polystyrene of 3 G000 to 4 G000. The composition and the conversion to poly(2) 1263118 styrene have a mass average molecular weight (Mw) of 3 000 to 700 phenolic enamel resin component (A2) 'and indicate the content of the component (A1) and the (A2) The mass ratio (A1) / (A2 ) 値 of the content of the component is 】 /] ~ 5 / 1. 5. The positive-type photoresist composition of claim 2, wherein the (A 1 ) component comprises a constituent unit derived from m-cresol and derived from 2,3,5-trimethylphenol. The constituent unit. 6. The positive-type photoresist composition according to claim 3, wherein the (A 2 ) component comprises a constituent unit derived from m-cresol and a constituent unit derived from p-cresol. 7. The positive resist composition according to claim 1, wherein the component (B) is a compound containing a phenolic hydroxyl group represented by the following formula (I). 8. The positive resist composition according to claim 1, wherein the component (c) is a compound containing a phenolic hydroxyl group represented by the following formula (n) and 1,2-naphthoquinonediazide Esterification reaction product of sulfonic acid compound (c 1 (3) 1263118 OH (H) 9. The positive resist composition according to claim 1, wherein the component (C) is a compound containing a phenolic hydroxyl group represented by the following formula (III) and 1,2-naphthoquinonediazidesulfonate. Esterification reaction product of acid compound (C2 (Melon) [wherein, R] to R8 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a carbon number of 3 to 6 a cycloalkyl group; R9 to R11 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Q is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a residue represented by the following chemical formula (IV); Base R 12 Μ (IV) (〇H)C (4) 1263118 (wherein R 2 and R 13 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, and a carbon number of 1 to 6; Alkoxy, or a cycloalkyl group having 3 to 6 carbon atoms; c is an integer representing from 1 to 3, or Q is bonded to R1 2 3 4 5 6 7 8 9 , R 9 , and between Q and R 9 The carbon atoms together form 3 to 6 cycloalkyl groups of the carbon chain; a and b are integers representing 1 to 3; d is an integer representing 0 to 3; and η is an integer representing 0 to 3. The positive resist composition of claim 1, wherein the component (C) is a compound containing a phenolic hydroxyl group represented by the following formula (V) and a 1,2-naphthoquinone Esterification reaction product of nitrogen sulfonic acid compound (C3 ch3 h3c -4 - 1 1 . The positive-type photoresist composition of claim 1 of the patent application, which is used for the manufacture of a liquid crystal display element. 3 1 2. A method for forming a photoresist pattern, which is characterized in that after coating a positive-type photoresist composition as in the scope of the patent application on the substrate 4, 5 pre-baking is used to form a photoresist film. a step of selectively exposing the photoresist film to the photoresist, and performing a development process on the photo-resist film after the selective exposure to form an alkali aqueous solution, and forming a photoresist pattern on the substrate. The photoresist pattern forming method of 8 steps, 9 the substrate is a low temperature polycrystalline 1263118 (5) germanium glass substrate having a low temperature polycrystalline germanium film on a glass substrate. 1 3. A method for forming a photoresist pattern according to claim 2, which is a step of performing a high-temperature post-baking at 200 ° C for the photoresist pattern after the development. 14. A positive-type resist composition according to claim 1 of the patent application, which is used for the manufacture of a liquid crystal display element.