KR20120110896A - Positive typed photosensitive composition comprising novle polyamide derivatives - Google Patents

Abstract

PURPOSE: A positive type photo-sensitive resin composition containing a polyamide derivative is provided to reduce the loss of a non-exposed part after development and to improve thermal stability. CONSTITUTION: A positive type photo-sensitive resin composition includes a polyamide derivative represented by chemical formula 1. In chemical formula 1, R1, R2, R4, and R5 are respectively divalent to hexavalent acyl groups with two or more carbon atoms; R3 is a hydrogen atom or a C1-10 alkyl group; k is the integer of 10 to 1000; l is the integer of 1 to 1000; n and m are respectively the integer of 0 to 2; the sum of n and m is more than 0; and X is a C2-30 carboxylic group.

Description

Positive type photosensitive resin composition containing a novel polyamide derivative {POSITIVE TYPED PHOTOSENSITIVE COMPOSITION COMPRISING NOVLE POLYAMIDE DERIVATIVES}

The present technology has a high sensitivity, a positive photosensitive resin composition which is easily crosslinked during the semiconductor process, has thermal stability, and reduces the loss of non-exposed areas after development, and a photoresist pattern film formed by curing of the photosensitive main composition. It is about.

In general, most photosensitive resin compositions used in semiconductor processes are positive photosensitive resin compositions in which an exposed portion is dissolved in an aqueous alkali solution by ultraviolet exposure. Generally, the composition comprises a resin that is dissolved in an aqueous alkali solution, a photosensitive compound that is insoluble in the aqueous alkali solution and sensitive to ultraviolet rays, and other additives.

Examples of the resin dissolved in the alkaline aqueous solution include polyamide derivatives. These resins are deformed into polyimide and polybenzoxazole by heat and have the characteristics of a heat resistant resin. The prior art used a composition having no photosensitivity, but recently, a trend toward a composition having a photosensitivity for the simplification of the process is a trend. The photosensitive resin composition made by using a conventional polyamide derivative has a poor thermal stability during crosslinking at 320 to 350 ^° C., resulting in a collapse of the pattern or a large decrease in volume. Therefore, a special crosslinking agent should be used. In this case, due to the properties of the compound having crosslinking properties, the resolution of the pattern is reduced or the degree of intermolecular crosslinking is severe during the crosslinking process, and thus the inherent characteristics of the polyimide resin are inferior in flexibility. In addition, these additives have a disadvantage in that the process time is long by decreasing the sensitivity during pattern formation.

In addition, in recent years, as the semiconductor process is complicated and various film thicknesses are required, the types of sulfonic acid esters included in the photosensitive resin composition and used as the photosensitive compound are also diversified. However, in the case of the sulfonic acid esters used previously, if the thickness is high, residues which remain in the bottom portion and do not dissolve in the developer are produced. When using a sulfonic acid ester having a good affinity with a developer to remove this, there is a disadvantage that a lot of non-exposed sites are lost. In addition, when the developing speed is lowered to prevent film loss of the non-exposed part, there is a problem in that much exposure energy is required.

The present invention provides a positive photosensitive resin composition having high sensitivity, easily crosslinked during a semiconductor process, having thermal stability, and reducing loss of non-exposed sites after development.

The positive photosensitive resin composition according to the embodiment of the present invention includes a polyamide derivative represented by the following general formula (1).

[Formula 1]

In formula (1), R ¹ , R ² , R ⁴ and R ⁵ are each independently a divalent to hexavalent acyl group having at least 2 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, k is each independently an integer of 10 to 1000, l is an integer of 1 to 1000, n and m are each independently an integer of 0 to 2 (where n + m> 0), X is 2 to 30 carbon atoms Carboxyl group. The polyamide derivative may include a compound represented by the following formula (2).

[Formula 2]

In formula (2), R ¹ and R ² are each independently a divalent to hexavalent acyl group having at least 2 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and p is a 10 to 1000 It is an integer, n and m are each independently the integer of 0-2 (where n + m> 0), and X is an acyl group of 2-30 carbon atoms.

The terminal of the polyamide derivative may further include an unsaturated bond site other than the carboxyl group.

The positive photosensitive resin composition includes, as a photosensitive compound, at least one naphthoquinone diazide sulfonic acid ester group (-ODNQ), and at least one alkylcarbonyl group or arylcarbonyl group having 1 to 8 carbon atoms in one molecule. To include a DNQ-sulfonic acid ester compound.

On the other hand, the positive photosensitive resin composition may further include a bis (4-hydroxy phenyl) fluorene compound in order to prevent the non-exposure site from melting during development.

The photoresist pattern film according to an embodiment of the present invention is a step of applying a positive photosensitive resin composition represented by the formula (1) on a substrate, drying, exposing the photosensitive resin composition, the photosensitive resin composition It can be formed by a process comprising the step of developing in an alkaline developer, and the heat treatment at a temperature of 320 to 350 ℃ the developed composition.

The positive photosensitive resin composition described above is cured to form a photoresist pattern film, and the photoresist pattern film remains in the device even after the semiconductor process or the display process is completed and can be used as an insulating film.

According to one embodiment of the present invention, the method for preparing a polyamide derivative of formula (1) is a step of converting a dicarboxylic acid derivative to a dichloride derivative using a cionyl chloride, and converting the converted dichloride derivative Condensation with the diamine derivative in the presence of a basic catalyst.

The condensation reaction may be performed at a temperature of −10 ° C. to 80 ° C.

The photoresist photosensitive resin composition according to an embodiment of the present invention not only has excellent sensitivity but also can be easily crosslinked during semiconductor processing, has excellent thermal stability, and can reduce the loss of non-exposed sites after development. Accordingly, by using the photosensitive resin composition, it is possible to manufacture a pattern film having improved verticality and excellent insulating properties, and thus it can be used as an insulating film of various semiconductor devices or display devices.

1 is a SEM photograph comparing before and after crosslinking of a patterned film prepared using the photosensitive resin composition obtained in Example 1. FIG.
FIG. 2 is a SEM photograph comparing before and after crosslinking of a patterned film prepared using the photosensitive resin composition obtained in Example 2. FIG.
3 is a SEM photograph comparing before and after crosslinking of a patterned film prepared using the photosensitive resin composition obtained in Example 3. FIG.
4 is a SEM photograph comparing before and after crosslinking of a patterned film prepared using the photosensitive resin composition obtained in Example 4. FIG.
5 is a SEM photograph comparing before and after crosslinking of a patterned film prepared using the photosensitive resin composition obtained in Example 5. FIG.
6 is a SEM photograph comparing before and after crosslinking of a patterned film prepared using the photosensitive resin composition obtained in Example 6. FIG.
7 is a SEM photograph comparing before and after crosslinking of a patterned film prepared using the photosensitive resin composition obtained in Example 7. FIG.
8 is a SEM photograph comparing before and after crosslinking of a patterned film prepared using the photosensitive resin composition obtained in Example 8. FIG.
9 is a SEM photograph comparing before and after crosslinking of a patterned film prepared using the photosensitive resin composition obtained in Example 9. FIG.
10 is a SEM photograph comparing before and after crosslinking of a patterned film prepared using the photosensitive resin composition obtained in Example 10. FIG.

Hereinafter, a positive photosensitive resin composition according to an embodiment of the present invention will be described in detail.

The photosensitive resin composition according to the embodiment of the present invention includes a polyamide derivative having a carboxyl group at its terminal. The positive photosensitive resin composition is highly sensitive and easily crosslinked, has thermal stability, and reduces the loss of non-exposed areas after development, thereby improving the verticality of the pattern and leading to good pattern formation.

The photosensitive resin composition may include a polyamide derivative, a photosensitive compound, and other additives represented by the following Formula 1.

[Formula 1]

In formula (1), R ¹ , R ² , R ⁴ and R ⁵ are each independently a divalent to hexavalent acyl group having at least 2 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, k is each independently an integer of 10 to 1000, l is an integer of 1 to 1000, n and m are each independently an integer of 0 to 2 (where n + m> 0), X is 2 to 30 carbon atoms Carboxyl group.

For example, the positive photosensitive resin composition may include a polyamide derivative represented by Formula 2 below.

[Formula 2]

In formula (2), R ¹ and R ² are each independently a divalent to hexavalent acyl group having at least 2 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and p is a 10 to 1000 It is an integer, n and m are each independently the integer of 0-2 (where n + m> 0), and X is a C2-C30 carboxyl group.

As a compound group which can be mentioned as said R <^1> , the compound group represented by following formula (3)-(23) is mentioned, for example, The following compound groups can be used individually or in combination of 2 or more.

 [Formula 3 to 23]

(3) (4) (5)

(6) (7) (8)

(9) (10) (11)

(12) (13) (14)

(15) (16) (17)

  (18) (19) (20)

               (21) (22)

               (23)

In Formula (17), R ⁶ may be a hydrogen atom, a halogen atom, a hydroxy group, a carboxy group, a thiol group or an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.

Meanwhile, in Chemical Formula 1, R ² may be a compound group represented by the following Chemical Formulas 24 to 38, and the following compound groups may be used alone or in combination of two or more thereof.

[Formula 24 to 38]

     (24) (25) (26)

(27) (28) (29)

 (30) (31) (32)

 (33) (34) (35)

 (36) (37) (38)

In Formula 34, R ⁷ may be a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a thiol group, or an alkyl group or an aryl group having 1 to 10 carbon atoms.

In the synthesis of the polymer of Formula (1), in order to improve molecular weight control and storage stability of the product, it is preferable to replace the amine group of the polymer backbone with a chemically stable functional group. There may be several ways to replace an amine group with another functional group. It is generally desirable to replace amine groups with amide groups. For example, a compound that reacts with an amine group to produce an amide group includes an alkylcarbonyl chloride derivative, an alkenylcarbonyl chloride derivative, an alkynylcarbonyl chloride derivative, an alkylsulfonyl chloride derivative, an arylsulfonyl chloride derivative, an alkyl group Acid anhydride derivatives, acid anhydride derivatives containing aryl groups, acid anhydride derivatives containing alkenyl groups, and the like. However, the use of alkylcarbonyl chloride derivatives or alkenylcarbonyl chloride derivatives having too fast chemical reaction among these compounds is a disadvantage of reacting not only with amine groups in the desired polymer backbone but also with other functional groups to produce byproducts. have. Therefore, in one embodiment of the present invention, the acid anhydride derivative is used to generate a carboxyl group after the reaction to give high sensitivity during development, and includes an unsaturated group in the derivative, and thus includes an acid anhydride derivative including an alkyl group having excellent thermal stability after crosslinking, and an aryl group. An acid anhydride derivative including an acid anhydride derivative containing an alkenyl group was used.

In the formula (1), X may be, for example, a compound group represented by the following formulas 39 to 46 as a functional group including a carboxyl group, but is not limited thereto, and may be used by mixing two or more kinds. As shown below, the following compounds further include at least one or more unsaturated bond sites other than carboxyl groups.

 [Formula 39 to 46]

    (39) (40) (41) (42)

(43) (44) (45) (46) (47

The polyamide derivative represented by the formula (1) can generally be produced by condensation reaction. The condensation reaction first converts the dicarboxylic acid derivative into a dichloride derivative using cionyl chloride, followed by condensation with the diamine derivative in the presence of a basic catalyst. The reaction temperature of the condensation reaction is preferably not more than 80 ^o C. If the temperature is too high, side products may be generated, which may inhibit the development speed and UV transmittance. However, if the temperature is less than -10 ^o C has a disadvantage that the reaction rate is slow. After the reaction is completed, the reaction mixture is slowly added dropwise to pure water, followed by precipitation to obtain a polymer compound in the form of a solid particle. If the molecular weight of the polymer is large, it can be controlled by increasing the amount of the acid anhydride derivative or sulfonyl chloride derivative that can react with the amine functional group.

The photosensitive compound according to the embodiment of the present invention includes at least one naphthoquinone diazide sulfonic acid ester group (-ODNQ) in one molecule, and at least one alkylcarbonyl group or arylcarbonyl group having 1 to 8 carbon atoms. DNQ-sulfonic acid ester compound. The DNQ-sulfonic acid ester compound may be included in the total composition in an amount of 5 to 30 parts by weight based on 100 parts by weight of the polyamide derivative.

More specifically, the DNQ-sulfonic acid ester compound may be represented by the following formula (47).

[Formula 47]

In Formula (47), R ₁ , R _2, and R ₃ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an ether group having 1 to 8 carbon atoms, an ester group having 1 to 8 carbon atoms, and 1 carbon atom. An alkylcarbonyl of 8 to 8 or an aryl carbonyl group of 6 to 8 carbon atoms, a thioether group of 1 to 8 carbon atoms, or a naphthoquinone diazide sulfonic acid ester group (-ODNQ), and R is represented by the following Chemical Formulas 1A to 1L At least one compound group selected from the group consisting of.

[Formulas 1A to 1L]

   (1A) (1B) (1C) (1D) (1E) (1F) (1G)

     (1H) (1I) (1J)

            (1K) (1L)

In the above formulas (1H) to (1L), R ₄ , R ₅ and R ₆ are each independently a divalent to hexavalent acyl group having at least two carbon atoms, and in formula (I), R ₇ is a hydrogen atom Or an alkyl group having 1 to 8 carbon atoms.

The photosensitive compound may be generated by substituting both the phenolic hydroxy group by using a DNQ group and an alkyl carbonyl group in order to maximize the dissolution inhibiting effect while minimizing the thickness reduction after development. In general, the DNQ group receives ultraviolet rays and is modified as shown in the following Reaction (1) to improve the transmittance to ultraviolet rays, but the residues remain on the substrate due to lower transmittance than the use of less DNQ groups.

[Reaction Scheme 1]

In one embodiment of the present invention, when reducing the substitution amount of DNQ to improve the permeability, there is a disadvantage in that the dissolution inhibiting effect is inferior to replace the remaining phenolic hydroxy group with an alkyl carbonyl group to compensate for this. Can be. The scheme is as follows.

 Scheme 2

In Scheme (2), R is an alkyl or aryl group having 1 to 8 carbon atoms. The amount of DNQ group and alkyl carbonyl or aryl carbonyl group in the above scheme can be arbitrarily controlled. However, when the DNQ group is substituted with 1 mole or less and the alkyl or aryl carbonyl group is substituted with 2 moles or more, the dissolution rate in the basic developer may be lowered, which may cause a disadvantage in that the development of the film having a high thickness does not occur to the bottom. If the DNQ group is substituted with 2.8 moles or more and the alkyl or aryl group is substituted with 0.2 moles or less, a disadvantage may occur that a residue may remain on the substrate after development. The most appropriate substitution amount of DNQ group is 1.0 mol to 2.8 mol. The substitution amount of DNQ can be suitably adjusted in consideration of the thickness, exposure energy, etc. of the film which used the composition.

The synthesis of the sulfonic acid ester can be carried out in a similar manner as the introduction of DNQ groups to compounds having two or more phenolic hydroxy groups. In some cases, the first reaction and the second reaction may be separated and reacted at the same time. A general reaction is to dissolve a compound having two or more phenolic hydroxyl groups and DNQ-Cl in a solvent, and then cool the mixture to 10 ° C or lower and then slowly add a basic catalyst. After the dropwise addition, the mixture was stirred at room temperature for a sufficient time, and then alkyl or aryl anhydride was added dropwise, and the basic catalyst was slowly added dropwise at 10 ° C. After dropping, the mixture was stirred at room temperature for a sufficient time, and then the reaction mixture was added dropwise to excess distilled water to obtain a product as a precipitate. The product obtained at this time is vacuum dried at 40 degrees C or less, and is used for preparation of a composition.

The total solids used in the composition depends on the thickness of the film required. The amount of sulfonic acid ester can be used from 5% to 50% based on the resin. The amount may vary depending on the rate at which the resin dissolves in the basic developer. When the dissolution rate in the developing solution is good, the content of sulfonic acid ester should be increased to prevent film loss at the unexposed areas.

Generally, in forming a pattern, basic pattern formation is possible only with the above-mentioned polyamide compound, diazonaptol compound, and solvent. However, recently, as the semiconductor device is highly direct, a composition requiring high resolution, high sensitivity, and little change in thickness after thermal crosslinking is required. In addition to the polyamide compound and diazonaphthol compound, other additives are required to obtain a composition having a minimum of high resolution, high sensitivity, and thickness change without deteriorating other physical properties. As a compound known to date, conventional low molecular phenol compounds were used. In the case of low molecular weight phenolic compounds, there is an advantage that can be easily obtained, while the thermal stability is low, when the thermal cross-linking at a high temperature of 300 ^° C or more often does not maintain the formed pattern. In order to overcome this problem, a phenol derivative having a methylol functional group or a separate thermal crosslinking agent is often used. If the thermal crosslinking agent is used separately, the thermal stability is maintained, but the crosslinked film has a disadvantage of inferior flexibility.

In the pattern formation process, bis (4-hydroxyphenyl) fluorene represented by the following general formula (48) may be used to prevent the non-exposed portion from being dissolved in the developer after exposure. In addition to preventing the non-exposure site from dissolving in the developer, this compound also plays a role in enhancing thermal stability after pattern curing.

(48)

In manufacturing this composition, in order to improve the adhesive force with a board | substrate, a silane coupling agent may be used. Alternatively, less than 5% diaminosiloxane may be used in the polymer backbone. When more than 5% of the polymer backbone diaminosiloxane monomer is used, heat resistance is inferior. As the silane coupling agent, vinyltrimethoxysilane, {3- (2-aminoethylamino) propyl} trimethoxysilane, 3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, 3-gly Cidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1 , 3-dimethylbutylidene) -3- (triethoxysilane) -1-propanamine, N, N-bis (3-trimethoxysilyl) propylethylamine, N- (3-trimethoxysilylpropyl) Pyrrole, ureidopropyltrimethoxysilane, (3-triethoxysilylpropyl) -t-butyl carbamate, N-phenylaminopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and the like. have. Among them, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, ureidopropyltrimethoxysilane, etc. are particularly excellent. 0.5-10 weight part is good with respect to 100 weight part of polyamide compounds. If less than this does not affect the adhesion improvement or more than this has the disadvantage that can inhibit the pattern formation or generate a scum (scum).

After patterning using the present composition, an etching process is performed to remove the lower passivation film. At this time, a corrosion inhibitor is added to protect the exposed aluminum film or the conductive wiring film from corrosion. Representative corrosion inhibitors include catechol derivatives, pyrogarol derivatives and alkyl gallate derivatives having a hydroxy group adjacent to the phenyl group. For example, the catechol, alkyl catechol, alkoxy catechol, pyrogarol, alkyl pyrogarol, alkoxy pyrogarol, alkyl gallate and the like are not particularly limited as long as the derivative has a hydroxyl group adjacent to the phenyl group. The amount of corrosion inhibitor to be used is 0.01 to 10% of the total composition. If less than this, there is a disadvantage that the anti-corrosion function is reduced, and if too much is used, the amount of loss of film during development is increased.

In addition, in order to improve coating properties, a surfactant, an antifoaming agent for removing bubbles, or the like may be used.

The positive photosensitive resin composition according to the embodiment of the present invention is prepared by dissolving the above-described compounds in a solvent. Commonly used solvents include gamma-butyrolactone, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, cyclohexane, 2-heptanone, propylene glycol monomethyl ether acetate, methyl isobutyl ketone , Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethyl lactate and the like. These solvents may be used alone or in combination of two or more solvents.

The method of forming a pattern using the said positive photosensitive resin composition is as follows. First of all, the composition is uniformly dissolved in a solvent and then filtered and coated on a silicon wafer or glass substrate to a desired thickness using a method such as rotary coating, spray coating, roll coating, or the like. The coated substrate is heated to 50-150 ^° C. using an oven, hot plate or infrared light to dry and remove the solvent. The film of the composition produced on the substrate is subjected to an exposure process using an i-line, h-line or g-line exposure machine. The substrate on which the mask pattern has been transferred may be transferred to a developing process, and then a pattern may be obtained through development, washing, and drying. Tetramethylammonium hydroxide is mainly used as the developing solution for the developing step, but it is not particularly limited as long as it is a compound having basic properties. The resulting pattern is placed in an oven at 280 ^° C. or higher and then heated for at least several ten minutes to convert it to a polyimide or polybenzoxazole compound, ie to induce crosslinking reactions. The crosslinking reaction temperature is preferably 320 to 350 ° C. The obtained film can be used as an intermediate protective film or the like in an interlayer insulating film or packaging process of a semiconductor or display process.

The present invention is excellent in crosslinkability and thermal stability, can reduce the loss of non-exposed areas after development, and enables the pattern formation with improved pattern verticality.

Although the photosensitive resin composition of this invention is demonstrated in detail with reference to the following Example, the technical thought of the following invention is not restrict | limited by the following Example. In the examples, organic solvents were dehydrated, and polymers were synthesized under a nitrogen atmosphere.

[Synthesis Example]

Synthesis Example 1

[4,4'-oxybisbenzoyl chloride synthesis]

In a 0.5 L flask equipped with a stirrer and a thermometer, 60 g (0.2324 mol) 4,4'-oxybis benzoic acid was added to 240 g N-methylpyrrolidone (NMP), stirred and dissolved, and the flask was cooled to 0 ° C. 110 g (0.9246 mol) of thionyl chloride was added dropwise and reacted for 1 hour to obtain a 4,4'-oxybis benzoic chloride solution.

Synthesis Example 2

[Polyamide A Synthesis / Polymer A]

Meanwhile, 400 g N-methylpyrrolidone (NMP) was placed in a 1 L flask equipped with a stirrer and a thermometer, and 85 g (0.2321 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added thereto. It was dissolved with stirring. Then 4,4'-oxybisbenzoyl chloride was slowly added dropwise and stirred at room temperature for 1 hour. The resulting solution was added to 3 liters of water, and the resulting precipitate was filtered, washed and dried in vacuo to give 128 g of polyamide A. The polyamide obtained at this time had a polystyrene reduced average molecular weight of 20,500.

Synthesis Example 3

[Polyamide B Synthesis / Polymer B]

Meanwhile, 400 g N-methylpyrrolidone (NMP) was placed in a 1 L flask equipped with a stirrer and a thermometer and 85 g (0.2321 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane were added. It was dissolved while stirring. Then pyridine 39g (0.4930mol) was added and 8g (0.0487mol) of 5-norbornene-2,3-dicarboxylic anhydride and 4,4'-oxybisbenzoyl chloride synthesized above were slowly added dropwise. Stir at room temperature for 1 hour. The resulting solution was added to 3 liters of water, and the resulting precipitate was filtered, washed and dried in vacuo to give 128 g of polyamide A. The polyamide obtained at this time had a polystyrene reduced average molecular weight of 19,300.

Synthesis Example 4

[Diazonaphthol Compound Synthesis / PAC A]

In a round flask, 50 g of tris (4-hydroxyphenyl) ethane and 132 g of 1,2-naphthoquinone diazide-5-sulfonyl chloride are dissolved in 900 g of dioxane and cooled with ice water. 48 g of triethylamine was slowly added dropwise to the solution at the same temperature, followed by stirring at room temperature for 8 hours. The solution is added dropwise to excess deionized water to form a precipitate. The formed precipitate is filtered off. Washed and dried in vacuo at 40 ° C. for 48 hours to give 118 g of sulfonic acid ester.

Synthesis Example 5

[Diazonaphthol Compound Synthesis / PAC B]

In a round flask, 50 g of tris (4-hydroxyphenyl) ethane, 87 g of 1,2-naphthoquinone diazide-5-sulfonyl chloride and 17 g of acetic anhydride were dissolved in 800 g of dioxane and cooled with ice water. 59 g of triethylamine was slowly added dropwise to the solution at the same temperature, followed by stirring at room temperature for 8 hours. The solution is added dropwise to excess deionized water to form a precipitate. The formed precipitate is filtered off. Washed and dried in vacuo at 40 ° C. for 48 hours to give 95 g of sulfonic acid ester.

Synthesis Example 6

[Diazonaphthol Compound Synthesis / PAC C]

In Synthesis Example 1, 91 g of sulphonic acid ester was obtained using 87 g of 1,2-naphthoquinone diazide-4-sulfonyl chloride instead of 87 g of 1,2-naphthoquinone diazide-5-sulfonyl chloride.

[Example]

Example 1

The synthesized polymer, the diazonapthol compound, and various additives were dissolved in the solvent, gamma-butyrolactone, to 40% by weight, and then particulate matter was removed using a 0.5um filter. The filtrate was spun onto an 8 inch silicon wafer to be 10 um thick. At this time, the baking was carried out at 130 degrees for 60 seconds to completely remove the solvent. The coated wafer was exposed to light using an exposure machine and developed at 2.38 wt% of tetramethyl ammonium hydroxide. The developed wafers were observed for resolution using an SEM (electron microscope). The thickness measured the film thickness before and behind exposure using a nanospec. SCUM remaining on the bottom of the developed site was confirmed by SEM. After cross-linking, the pattern shapes were classified into top, top, middle, and bottom in the SEM in consideration of verticality and mask shape fidelity. In addition, as the additive used in the examples, the compound of the formula (48) was used.

Examples 2 to 10

Examples 2 to 10 were used in the same manner as in Example 1, but each pattern was formed in the composition shown in Tables 1-3.

 Example 1  Example 2  Example 3  Example 4  Polymer A  34 g  34 g  30 g  30 g  Polymer B  -  -  -  -  PAC A  6 g  -  6 g  -  PAC B  -  6 g  -  6 g  PAC C  -  -  -  -  additive  -  -  4 g  4 g  menstruum  60 g  60 g  60 g  60 g

 Example 5  Example 6  Example 7  Example 8  Polymer A  -  -  -  -  Polymer B  30 g  30 g  30 g  30 g  PAC A  6 g  -  6 g  -  PAC B  -  6 g  -  6 g  PAC C  -  -  -  -  additive  -  -  4 g  4 g  menstruum  60 g  60 g  60 g  60 g

 Example 9  Example 10  Polymer A  -  -  Polymer B  30 g  30 g  PAC A  PAC B  PAC C  6 g  6 g  additive  4 g  menstruum  60 g  60 g

[Test result]

Based on the results of the pattern formation using the photosensitive resin composition obtained in each example, the properties of sensitivity, residual film ratio, resolution, and pattern shape were measured and evaluated. The results are shown in Tables 4 and 5 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Sensitivity 320 mJ / cm ² 300mJ / cm ² 290 mJ / cm ² 260mJ / cm ² 280mJ / cm ² Residual film ratio 90% 88% 87% 88% 86% resolution 5um 5um 5um 5um 5um Pattern form medium Prize Prize Prize Prize

Example 6 Example 7 Example 8 Example 9 Example 10 Sensitivity 260mJ / cm ² 240mJ / cm ² 240mJ / cm ² 240mJ / cm ² 210mJ / cm ² Residual film ratio 88% 90% 89% 89% 88% resolution 5um 5um 5um 5um 5um Pattern form Prize the best Prize the best the best

 [Observation of pattern film after crosslinking]

The patterns formed in Examples 1 to 10 were crosslinked by heat treatment at a temperature of 330 ° C., and pattern patterns before and after crosslinking were observed in the process.

1 to 10 are SEM photographs comparing the pattern film before and after crosslinking of the photoresist pattern formed in each example. 1 to 10, the pattern film prepared using the photosensitive resin composition obtained in each of the embodiments of the present invention is excellent in the verticality of the pattern, in particular the vertical of the pattern film after crosslinking of Examples 5 to 10 It can be seen that the characteristics are more excellent.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.

Therefore, it should be understood that the above-described embodiments are provided so that those skilled in the art can fully understand the scope of the present invention. Therefore, it should be understood that the embodiments are to be considered in all respects as illustrative and not restrictive, The invention is only defined by the scope of the claims.

Claims (10)

Positive photosensitive resin composition containing the polyamide derivative represented by following General formula (1):

(One)
In formula (1), R ¹ , R ² , R ⁴ and R ⁵ are each independently a divalent to hexavalent acyl group having at least 2 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, k is each independently an integer of 10 to 1000, l is an integer of 1 to 1000, n and m are each independently an integer of 0 to 2 (where n + m> 0), X is 2 to 30 carbon atoms Carboxyl group.
The method of claim 1,
The polyamide derivative is a positive photosensitive resin composition, characterized in that it comprises a compound represented by the following formula (2):

(2)
In formula (2), R ¹ and R ² are each independently a divalent to hexavalent acyl group having at least 2 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and p is a 10 to 1000 It is an integer, n and m are each independently the integer of 0-2 (where n + m> 0), and X is a C2-C30 carboxyl group.
The method of claim 1,
The terminal of the polyamide derivative is a positive photosensitive resin composition, characterized in that it further comprises an unsaturated bond site other than the carboxyl group.
The method of claim 1,
As a photosensitive compound, a DNQ-sulfonic acid ester compound comprising at least one naphthoquinonediazide sulfonic acid ester group (-ODNQ) and at least one alkylcarbonyl group or arylcarbonyl group having 1 to 8 carbon atoms in one molecule A positive photosensitive resin composition comprising the same.
The method of claim 4, wherein
The positive photosensitive resin composition, wherein the DNQ-sulfonic acid ester compound is a compound represented by the following Formula (47):

(47)
In Formula (47), R ₁ , R _2, and R ₃ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an ether group having 1 to 8 carbon atoms, an ester group having 1 to 8 carbon atoms, and 1 carbon atom. An alkylcarbonyl of 8 to 8 or an aryl carbonyl group of 6 to 8 carbon atoms, a thioether group of 1 to 8 carbon atoms, or a naphthoquinone diazide sulfonic acid ester group (-ODNQ), and R is represented by the following Chemical Formulas 1A to 1L At least one compound group selected from the group consisting of.

(1A) (1B) (1C) (1D) (1E) (1F) (1G)

(1H) (1I) (1J)

(1K) (1L)
(In the above formulas (1H) to (1L), R ₄ , R ₅ and R ₆ are each independently a divalent to hexavalent acyl group having at least two carbon atoms, and in formula (I), R ₇ is hydrogen Atoms or alkyl groups of 1 to 8 carbon atoms)
The method of claim 1,
Positive type photosensitive resin composition characterized by containing a bis (4-hydroxy phenyl) fluorene compound in order to prevent a non-exposure part melt | dissolved in the image development process. Applying the positive photosensitive resin composition of claim 1 on a substrate and drying the substrate;
Exposing the photosensitive resin composition;
Developing the photosensitive resin composition in an alkaline developer; And
Method for producing a photoresist pattern film comprising the step of heat-treating the developed composition at a temperature of 320 to 350 ℃.
A pattern film formed by curing the positive photosensitive resin composition of claim 1, wherein the photoresist pattern film is used as an insulating film after the semiconductor process or the display process is completed.
Converting the dicarboxylic acid derivative to the dichloride derivative using cionyl chloride; And
Condensation of the converted dichloride derivatives with diamine derivatives in the presence of a basic catalyst.

(One)
(In Formula (1), R ¹ , R ² , R ⁴ and R ⁵ are each independently a divalent to hexavalent acyl group having at least 2 carbon atoms, and R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. and k are each independently an integer of 10 to 1000, l is an integer of 1 to 1000, n and m are each independently an integer of 0 to 2 (where n + m> 0), and X is 2 to C 30 carboxyl groups)
10. The method of claim 9,
The condensation reaction is a method for producing a polyamide derivative, characterized in that at a temperature of -10 ℃ to 80 ℃.

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