KR100914063B1 - Positive type photosensitive resin composition - Google Patents

Abstract

The present invention relates to a positive photosensitive resin composition, which comprises: (A) a polyamide polymer represented by the following general formula (1); (B) esterified quinonediazide compounds; (C) phenol group containing compound; And (D) a solvent.

[Formula 1]

(In the above formula, the definition of each substituent is as defined in the specification.)

When the lithography process is performed using the positive type photosensitive resin composition of the present invention, chemical change is caused by exposure, and the development speed of the exposed area can be increased to form a pattern, and after curing, the degree of crosslinking is increased to increase the resolution and sensitivity. It is possible to form a surface protective film or an interlayer insulating film having excellent heat resistance while minimizing losses.

Positive photosensitive composition, polyamide, semiconductor element protective film, insulating film, phenolic hydroxyl group, aqueous alkali solution, imine, terminal group

Description

Positive type photosensitive resin composition {POSITIVE TYPE PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a positive photosensitive resin composition, and more particularly, to a positive photosensitive resin composition capable of obtaining a pattern having high sensitivity and high resolution and having excellent heat resistance.

In recent years, as semiconductor devices have been increasingly integrated, enlarged, thinned, and miniaturized, wiring and isolation widths required in the manufacturing process have become very fine. As a result, a resin composition having high resolution and high sensitivity is required for the surface protective film and the interlayer insulating film of the semiconductor element. In addition, in order to serve as a surface protective film and an interlayer insulating film, a resin composition having excellent heat resistance and excellent electrical and mechanical properties is required. The pattern formation technology of the surface protective film and the resin composition for an interlayer insulating film having such high sensitivity and high resolution and excellent heat resistance has become a core and serves as a traction difference for ultra-high integration of semiconductors.

A typical positive photosensitive resin composition is the addition of esterified quinonediazide, which exhibits photosensitivity, to a polyamide polymer. In the usual pattern formation process using this composition, the photosensitive resin composition is first exposed to light of a specific wavelength in a pattern manner to be exposed. At this time, at the exposed site, the esterified quinonediazide compound undergoes chemical change and is converted to the carboxylic acid form. The exposed film is then contacted with any material (typically an aqueous alkaline developer). The portion of the composition containing the converted carboxylic acid is selectively developed in alkaline solution due to increased solubility in the developer. The temperature of the patterned layer is then increased to form a cured pattern.

In the technology of the surface protective film or the interlayer insulating film, development of both a patterning material having high resolution and high sensitivity optical properties and a composition material having high heat resistance and excellent mechanical properties after curing are required. However, in order to improve the optical properties, it is necessary to design such that the content of the aromatic compound is low, the crosslinking degree is low at low molecular weight and the flowability is good. It is difficult to develop a material that satisfies the conflicting physical properties due to high and low fluidity.

In particular, in the existing polyamide, there is a limit to the development of a high characteristic photosensitive resin composition due to the inverse relationship between the pattern refining properties and the film properties after curing. In an attempt to overcome this limitation, a photosensitive resin composition has been studied that minimizes the cured film characteristics such as heat resistance while increasing the resolution by substituting the terminal of polyamide with arylcyclic.

However, such a photosensitive resin composition also has a problem in that it still fails to meet the required physical properties due to the miniaturization of the pattern and the demand for excellent high mechanical properties due to the improved integration of semiconductor devices. Therefore, there is a need for development of a new type of photosensitive resin material that overcomes the limitations of existing materials.

An object of the present invention is to provide a positive photosensitive resin composition capable of forming a fine pattern and having excellent heat resistance and obtaining a pattern of high sensitivity and high resolution.

Another object of the present invention is to provide a method for producing a photosensitive pattern using the composition.

Still another object of the present invention is to provide an electronic component for a semiconductor manufactured using the resin composition.

Technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

A first embodiment of the present invention for achieving the above object is (A) a polyamide polymer represented by the following formula (1); (B) esterified quinonediazide compounds; (C) phenol group containing compound; And (D) a solvent for providing a positive photosensitive resin composition.

[Formula 1]

(Wherein

X ₁ to X ₃ are independently a divalent to tetravalent organic group,

Y ₁ to Y ₂ are independently a divalent to hexavalent organic group,

E is a residue derived from an aldehyde,

R ₁ to R ₂ are each independently hydrogen or an organic group having 1 to 5 carbon atoms,

m1 and m2 are each independently 0 to 100 as an average value, m1 + m2 is 5 to 100,

n1, n2 and n3 are each independently an integer of 0 to 2, n2 + n3 is an integer of 0 to 3)

A second embodiment of the present invention is to provide an electronic component for a semiconductor comprising a photosensitive resin film prepared using the positive photosensitive resin composition.

Other specific details of embodiments of the present invention are included in the following detailed description.

When the lithography process is performed using the positive type photosensitive resin composition of the present invention, chemical change is caused by exposure, and the development speed of the exposed part can be increased to form a pattern, and after curing, the degree of ring closure and crosslinking is increased. It is possible to form a surface protective film or an interlayer insulating film having excellent heat resistance while minimizing loss of resolution and sensitivity.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

The present inventors have found that when the polyamide terminal is substituted with imine, the membrane properties such as high heat resistance can be enhanced while maintaining high sensitivity pattern characteristics.

Positive type photosensitive resin composition according to the first embodiment of the present invention is (A) polyamide represented by the following formula (1); (B) esterified quinonediazide compounds; (C) a phenol group containing compound and (D) solvent.

The polyamide has an end portion substituted with imine, and after coating the composition to form a coating film, selectively exposing the amide to a carboxylic acid to cause a chemical change of an esterified quinonediazide compound, a photosensitive agent, in the exposed portion. And polymers which are thereby formed so that the solubility in the developer is increased to selectively form a soluble region, which is cured by temperature or catalyst to be closed and crosslinked.

Hereinafter, each component will be described in detail.

(A) Polyamide  Polymer

The polyamide polymer of the present invention is preferably represented by the following formula (1).

[Formula 1]

Where

X ₁ to X ₃ are independently a divalent to tetravalent organic group,

Y ₁ to Y ₂ are independently a divalent to hexavalent organic group,

And E is a residue derived from aldehyde, Any aldehyde may be used as the aldehyde, but in particular, the aryl cyclic form cyclohexyl carboxaldehyde, norbornane carboxaldehyde, norbornene carboxaldehyde, and adamantyl carboxaldehyde ( adamantyl carboxaldehyde), isobornyl carboxaldehyde and the like are preferred and may be used alone or in combination of two or more thereof.

R ₁ to R ₂ are each independently hydrogen or an organic group having 1 to 5 carbon atoms,

m1 and m2 are each independently 0 to 100 as an average value, m1 + m2 is 5 to 100,

n1, n2 and n3 are each independently an integer of 0 to 2, and n2 + n3 is an integer of 0 to 3;

The polyamide polymer of Chemical Formula 1 is prepared by reacting a dicarboxylic acid monomer selected from the group consisting of dicarboxylic acid anhydride, dicarboxylic acid and derivatives thereof with a diamine monomer, and reacting the obtained reaction product with an aldehyde. Can be. In the process of reacting the reaction product with the aldehyde, the terminal amine group of the reaction product is converted into an imine group.

The diamine monomer may be preferably represented by X (NH ₂ ) ₂ (OH) _{n 1} (where n 1 is an integer of 0 to 2).

Examples of the diamine monomers include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, para-phenylene Aromatic amines of diamine, meta-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine; A compound in which the aromatic ring is substituted with an alkyl group or a halogen atom in the aromatic amine; Aliphatic cyclohexyl diamine, methylenebiscyclohexylamine, etc. are mentioned. 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxysulfone, 4,4'-diamino-3, 3'-dihydroxyphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- ( 3-amino-4-hydroxyphenyl) hexafluoropropane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxy Benzophenone, 4,4'-diamino-3,3'-dihydroxydiphenylether 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-di Although hydroxybenzene etc. are mentioned, It is not limited to these. In addition, these diamine monomers can be used individually or in mixture. As the diamine monomer, more preferably 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,3'-diamino-4,4'-dihydroxysulfone and mixtures thereof.

X may preferably include a structure of the following Chemical Formulas 4 to 15, but is not necessarily limited thereto.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

Wherein A and B are each independently of the other -C-, C (CH ₃ ) _2- , -S-, -O-, -SO _2- , -CO-, -CONH-, C (CF ₃ ) ₂ -Or a single bond)

In addition, a silicone-containing diamine monomer may be used together with such a silicone-free diamine monomer. It is preferable to further use the silicone-containing diamine monomer because the adhesion to the substrate can be enhanced. Examples of the silicone-containing diamine monomers include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (p-aminophenyl) tetramethyldisiloxane, bis- (gamma-aminopropyl) tetra Methyl disiloxane, 1, 4-bis (gamma-aminopropyl dimethyl silyl) benzene, etc. are mentioned, It is not limited to these. Among them, bis (4-aminophenyl) tetramethylsiloxane, bis (p-aminophenyl) tetramethyldisiloxane or a combination thereof can be more preferably used.

At this time, in order to increase the adhesive force with the upper and lower membrane layer, it is preferable to use so that the ratio of the silicon-containing diamine monomer to the silicon-free diamine monomer is 0.1 to 10% by weight. When the amount of the silicon-containing diamine monomer is less than 0.1%, the adhesive strength with the upper and lower layer is insufficient, and when the amount of the silicon-containing diamine monomer exceeds 10%, there is a problem that may damage the optical properties and the film properties.

The dicarboxylic acid monomer may be represented by Y (COOH) ₂ (COOR) _n2 (OH) _n3 , where Y is a divalent to hexavalent organic group, n2 and n3 are independently integers of 0 to 2 Examples thereof include dicarboxylic dianhydride or dicarboxylic acid derivative. Specific examples of the dicarboxylic dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4-biphenyltetracarboxylic acid Dianhydrides, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydrides, 1,1-bis (2,3-dicarboxyphenyl) Ethane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, and the like. In addition, as the dicarboxylic acid derivative, an active compound which is an active ester-type derivative in which chloride or 1-hydroxy-1,2,3-benzotriazole is reacted in advance may be used, and specific examples thereof include diphenyloxydicar Acid chloride, bis (phenylcarboxylic acid chloride) sulfone, bis (phenylcarboxylic acid chloride) ether, bis (phenylcarboxylic acid chloride) phenone, phthalic carboxylic acid dichloride, diphenyloxydicarboxylate benzotria Sol and the like.

Particularly preferred dicarboxylic acid monomers are 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, diphenyloxydicarboxylic acid chloride Phthalic carboxylic acid dichloride and the like, but are not limited thereto.

Y may preferably include structures of the following Chemical Formulas 4 to 6 and 11 to 15, but is not necessarily limited thereto.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

Wherein A and B are each independently of the other -C-, C (CH ₃ ) _2- , -S-, -O-, -SO _2- , -CO-, -CONH-, C (CF ₃ ) ₂ -Or a single bond)

The polyamide polymer represented by Chemical Formula 1 may be a copolymer in which two or more monomers are polymerized within the range of not impairing the water solubility of the homopolymer or polymer composed of an amide bond unit or polymer. Various patterns are possible as the copolymer, and for example, a random copolymer, a block copolymer, and a graft copolymer may be used, but a random copolymer is preferable. That is, in Chemical Formula 1, X ₂ to X ₃ ; Or Y1 to Y ₂ ; Or a copolymer in which two or more monomers having different R ₁ to R ₂ from each other are polymerized, wherein X ₂ to X ₃ ; Or Y ₁ to Y ₂ ; Alternatively, the present invention may be present as a block, a graft, or a random copolymer according to the order of R ₁ to R ₂ or the values of m ₂ and m ₁ , which are well known in the art, and thus a detailed description thereof will be omitted.

The molecular weight of the polyamide polymer represented by Formula 1 may be arbitrarily selected within a range that does not impair the effects of the present invention, but in order to maximize the effect of post-exposure pattern generation while ensuring effective solubility and coating property, It is preferable that Mw) is 500-500,000, More preferably, it is preferable that the weight average molecular weights are 1,000-50,000. If the weight average molecular weight is less than 1,000, it is not preferable because sufficient physical properties are not obtained. If the weight average molecular weight is more than 50,000, the solubility in organic solvents becomes low and handling becomes very difficult.

(B) esterified quinonediazide compounds

The esterified quinonediazide compound is a compound serving as a photo active compound (PAC), and a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure can be used. . This is a material known from US Pat. Nos. 2,772,972, 2,797,213, 3,669,658 and the like.

Preferred esterified quinonediazide compounds in the present invention are compounds represented by the following formulas (2) to (3).

[Formula 2]

[Formula 3]

또는

임).Where Q is

or

being).

In the positive photosensitive resin composition of the present invention, the content of the esterified quinonediazide compound (PAC) is preferably 1 to 50 parts by weight, more preferably 5 to 30 parts by weight based on 100 parts by weight of the polyamide polymer. When the content of the PAC is included in 1 to 50 parts by weight, the pattern is well formed without residue by exposure, and there is no loss of film thickness during development, and a good pattern can be obtained.

(C) phenol group containing compound

The phenol group-containing compound included in the positive photosensitive resin composition of the present invention increases the dissolution rate in the exposed portion and serves to improve the sensitivity. Examples of such phenol group-containing compounds include 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, and the like. It may be, but is not limited thereto.

The content of the phenol group-containing compound in the positive photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the polyamide polymer. When the content of the phenol group-containing compound is in the range of 0.1 to 30 parts by weight, a good pattern can be obtained by appropriately increasing the dissolution rate of the non-exposed part without causing sensitivity deterioration during development, and precipitation does not occur during freezing storage. It is preferable because it shows excellent storage stability.

(D) solvent

The positive photosensitive resin composition of this invention contains an organic solvent.

Examples of the solvent include N-methyl-2-pyrrolidone, gamma-butyrolactone, N, N-dimethyl acetate, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, methyl lactate, ethyl lactate, Methyl-1, 3- butylene glycol acetate, 1, 3- butylene glycol-3-monomethyl ether, etc. are mentioned, These can also be used individually or in mixture.

In this case, the amount of the organic solvent may be used in a 20:80 to 90:10 weight ratio with the polyamide polymer in the photosensitive resin composition. When the usage-amount of an organic solvent is contained in this range, the film | membrane of sufficient thickness can be coated and it is preferable because it is excellent in solubility and coating property.

The photosensitive resin film using the positive photosensitive resin composition according to the first embodiment of the present invention is manufactured by the following method. This manufacturing method includes the steps of applying the positive photosensitive resin composition on a support substrate and drying to form a resin film; Exposing the resin film; Developing the exposed resin film with an alkaline developer; And heat-processing the developed resin film.

Hereinafter, each manufacturing process will be described in detail.

The photosensitive resin film according to the present invention will be described in detail below with reference to FIGS. 1A to 1D, for example, in which a pattern is formed by an i-line light source among UV light sources.

Figures 1a to 1d is applied to the photosensitive resin composition of the present invention on the surface of the lower film, the exposure to cause a chemical change of the resin composition to increase the dissolution rate of the exposed portion to be developed in an alkaline solution to form a pattern and heated to cure A conceptual diagram for explaining the steps in order.

As shown in FIG. 1A, the photosensitive resin composition of this invention is apply | coated on the to-be-processed substrate 1, such as a semiconductor substrate, for example, and the photosensitive resin composition layer 2 is formed.

Subsequently, an i-line light source is irradiated using a photomask (not shown) to expose the resin composition layer 2. According to this exposure process, the photosensitive agent of the composition layer located in the exposure part 3 selectively changes chemically (FIG. 1B), and the photosensitive agent of the composition layer located in the non-exposed part 4 does not produce chemical change. Next, as shown in FIG. 1C, the exposed resin composition layer is subjected to a developing step using an aqueous alkali solution as a developer. According to this developing process, the exposure part 3 of the resin composition layer which the said chemical change generate | occur | produced is removed, and the patterned resin composition layer 5 is obtained. Then, the patterned photosensitive resin composition layer 5 is heated (FIG. 1D). According to the heating process, the pattern layer of the resin composition is cured to form the photosensitive resin film 6.

A second embodiment of the present invention is to provide an electronic component for a semiconductor comprising a photosensitive resin film prepared using the positive photosensitive resin composition according to the first embodiment of the present invention. The photosensitive resin film may be used as a surface protective film or an interlayer insulating film. As such, the positive photosensitive resin composition of the present invention may be usefully used to form a surface protective film or an interlayer insulating film in a semiconductor electronic component, and in addition, it may be used in various fields for obtaining a pattern having a high sensitivity and a high resolution as a positive type. have.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Synthesis Example 1 Synthesis of Polyamide Polymer (P-1) (Mw = 10K)

18.3 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injection device, and a cooler. 280 g of methyl-2-pyrrolidone (NMP) was added and dissolved.

When the solid is completely dissolved, 9.9 g of pyridine is added to the obtained solution, and 14.8 g of 4,4'-oxydibenzoyl chloride is added thereto with N-methyl-2-pyrrolidone while maintaining the temperature of the obtained solution at 5 ° C. (NMP) 142 g of the dissolved solution was slowly added dropwise to the solution for 30 minutes. After dropping, the reaction was carried out at a temperature of 5 ° C. for 1 hour, the temperature was raised to room temperature, stirred for 1 hour, 0.5 g of acetic acid and 1.5 g of cyclohexyl carboxaldehyde were added, followed by stirring for 1 hour.

The reaction mixture was poured into a solution of water / methanol = 10/1 (volume ratio) to form a precipitate, and the precipitate was filtered and sufficiently washed with water. The polyamide polymer (P-1) was prepared by drying at a temperature of 80 ° C. under vacuum for at least 24 hours.

Synthesis Example 2 Synthesis of Polyamide Polymer (P-2) (Mw = 10K)

A polyamide polymer (P-2) having a weight average molecular weight of 10 K was prepared in the same manner as in Synthesis Example 1, except that 1.5 g of norbornene carboxaldehyde was used instead of cyclohexyl carboxaldehyde.

Synthesis Example 3 Synthesis of Polyamide Polymer 3 (Mw = 9K)

17.4 g, 1,3 hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injector and a cooler 0.86 g of bis (aminopropyl) tetramethyldisiloxane was added, and 280 g of N-methyl-2-pyrrolidone (NMP) was added thereto to dissolve it.

When the solid was completely dissolved, 9.9 g of pyridine was added, and 13.3 g of 4,4'-oxydibenzoyl chloride was added thereto while maintaining the temperature of the obtained solution at 0 to 5 ° C. NMP) was added dropwise into the solution of 142 g and slowly dissolved for 30 minutes. After dropping, the reaction was carried out at a temperature of 5 ° C. for 1 hour, and the reaction was carried out for 1 hour by raising the temperature to room temperature. 1.5 g of cyclohexyl carboxaldehyde was added thereto, followed by stirring at room temperature for 2 hours to complete the reaction.

The reaction mixture was poured into a solution of water / methanol = 10/1 (volume ratio) to form a precipitate, and the precipitate was filtered and sufficiently washed with water. The polyamide polymer (P-3) was prepared by drying at a temperature of 80 ° C. under vacuum for at least 24 hours.

Synthesis Example 4 Synthesis of Polyamide Polymer (P-4) (Mw = 9K)

Polyamide polymer (P-4) having a weight average molecular weight of 9K was prepared in the same manner as in Synthesis Example 3, except that 1.5 g of norbornene carboxaldehyde was used instead of cyclohexyl carboxaldehyde.

Synthesis Example 5 Synthesis of Polyamide Polymer 5 (Mw = 10K)

18.3 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injection device, and a cooler. 280 g of methyl-2-pyrrolidone (NMP) was added and dissolved.

When the solid was completely dissolved, 9.9 g of pyridine was added, while 11.8 g of 4,4'-oxydibenzoyl chloride and 2.5 g of phthalic chloride were added thereto while maintaining the temperature of the obtained solution at 5 ° C. The solution dissolved in 142 g of pyrrolidone (NMP) was slowly added dropwise for 30 minutes. After dropping, the reaction was carried out at a temperature of 5 ° C. for 1 hour, the temperature was raised to room temperature, stirred for 1 hour, 0.5 g of acetic acid and 1.5 g of cyclohexyl carboxaldehyde were added, followed by stirring for 1 hour.

The reaction mixture was poured into a solution of water / methanol = 10/1 (volume ratio) to form a precipitate, and the precipitate was filtered and sufficiently washed with water. The polyamide polymer (P-5) was prepared by drying at a temperature of 80 ° C. under vacuum for at least 24 hours.

Synthesis Example 6 Synthesis of Polyamide Polymer (P-6) (Mw = 10K)

A polyamide polymer (P-6) having a weight average molecular weight of 10 K was prepared in the same manner as in Synthesis Example 6, except that 1.5 g of norbornene carboxaldehyde was used instead of cyclohexyl carboxaldehyde.

Synthesis Example 7 Synthesis of Polyamide Polymer (P-7) (Mw = 10K)

A polyamide polymer (P-7) having a weight average molecular weight of 10 K was prepared in the same manner as in Synthesis Example 1, except that 1.5 g of maleic anhydride was used instead of cyclohexyl carboxaldehyde.

Synthesis Example 8 Synthesis of Polyamide Polymer (P-8) (Mw = 10K)

Polyamide polymer (P-8) having a weight average molecular weight of 10 K using the same method as in Synthesis Example 1, except that 1.5 g of 5-norbornene-2,3-dicarboxylic hydride was used instead of cyclohexyl carboxaldehyde Was prepared.

[Examples 1 to 12]

Polyamide polymer synthesized in Synthesis Examples 1 to 6, esterified quinonediazide compound (PAC), phenol group-containing compound (2,6-diacetoxy methyl-p-cresol) and solvent (gamma-butyro) Lactone: GBL) was mixed at the composition ratios shown in Table 1 below to prepare a positive photosensitive resin composition.

인 것을 나타내며,In Table 1, PAC is 1a is a compound of Formula 2, Q is

Indicates that

것을 나타낸다.1b is a compound of Formula 2, wherein Q is

Indicates.

[Formula 2]

Example Polyamide polymer PAC 2,6-diacetoxy methyl-p-cresol Solvent (GBL) One 10 g, synthesis example 1 1a, 2 g 1 g 20 g 2 10 g, synthesis example 1 1b, 2 g 1 g 20 g 3 10 g, synthesis example 2 1a, 2 g 1 g 20 g 4 10 g, synthesis example 2 1b, 2 g 1 g 20 g 5 10 g, synthesis example 3 1a, 2 g 1 g 20 g 6 10 g, synthesis example 3 1b, 2 g 1 g 20 g 7 10 g, synthesis example 4 1a, 2 g 1 g 20 g 8 10 g, synthesis example 4 1b, 2 g 1 g 20 g 9 10 g, synthesis example 5 1a, 2 g 1 g 20 g 10 10 g, synthesis example 5 1b, 2 g 1 g 20 g 11 10 g, Synthesis Example 6 1a, 2 g 1 g 20 g 12 10 g, Synthesis Example 6 1b, 2 g 1 g 20 g

[Comparative Examples 1 to 4]

The polyamide polymer, PAC, phenol group-containing organic compound and solvent prepared in Synthesis Examples 7 and 8 were mixed in the composition shown in Table 2 to prepare a photosensitive resin resin composition. In Table 2 below, the definition of PAC is the same as in Table 1.

Comparative example Polyamide polymer PAC 2,6-diacetoxy methyl-p-cresol Solvent (GBL) One 10 g, Synthesis Example 7 1a, 2 g 1 g 20 g 2 10 g, Synthesis Example 7 1b, 2 g 1 g 20 g 3 10 g, Synthesis Example 8 1a, 2 g 1 g 1 g 4 10 g, Synthesis Example 8 1b, 2 g 1 g 1 g

[Examples 13 to 24]

Using the photosensitive resin composition prepared in Examples 1 to 12 as the resin composition for forming the micropattern, respectively, the lithography experiment was carried out in the following manner, and the results were named as Examples 13 to 24 and shown in Table 3 below. .

First, each of the positive photosensitive resin compositions prepared in Examples 1 to 12 was coated on a silicon wafer and prebaked at 120 ° C. for 200 seconds. The silicon wafer coated with the photosensitive resin composition was exposed using a Nikoni10c i-line stepper exposure apparatus and developed for 2 minutes with a 2.38% aqueous tetramethylammonium hydroxide (TMAH) solution. Subsequently, the plate was immersed in distilled water for 1 minute, washed, and then measured by using FE-SEM.

Sensitivity was determined as the optimum exposure time by obtaining an exposure time in which a 10 um L / S pattern was formed with a line width of 1 to 1 after exposure and development. The resolution made the minimum pattern dimension in the said optimal exposure time into the resolution.

After the pattern was formed, the mixture was heated at 120 ° C. for 30 minutes in a nitrogen atmosphere, and then heated to 320 ° C. for 1 hour, and heated at 320 ° C. for 1 hour to prepare a cured film.

Thereafter, the cured film immersed in an aqueous 2% hydrogen fluoride solution and peeled from the silicon wafer was sufficiently washed with water, dried, and 5 wt% weight loss temperature was measured by thermal weight analysis (TGA).

Sample Sensitivity (mJ / cm ² ) Resolution (um) 5 wt% weight loss temperature (℃) Example 13 500 5 550 Example 14 400 5 510 Example 15 390 7 520 Example 16 480 5 550 Example 17 440 3 560 Example 18 420 7 550 Example 19 420 5 520 Example 20 470 3 520 Example 21 380 7 560 Example 22 510 3 560 Example 23 480 5 560 Example 24 480 5 550

As can be seen from the results of Table 3, the sensitivity value is 510 mJ / cm ² or less and the resolution value is 7 or less, and the optical properties are excellent, and the 5 wt% weight loss temperature also shows high heat resistance over 500 ° C. can confirm. This is believed to be due to the effect of replacing the terminal of the polyamide polymer with an imine group.

[Comparative Examples 5 to 8]

Except for using the photosensitive resin composition prepared in Comparative Examples 1 to 4 after the lithography experiment in the same manner as in Example 13, the results are shown in Table 4 named Comparative Examples 5 to 8.

Sample Sensitivity (mJ / cm ² ) Resolution (um) 5 wt% weight loss temperature (℃) Comparative Example 5 700 5 440 Comparative Example 6 660 7 460 Comparative Example 7 680 7 460 Comparative Example 8 720 5 460

As can be seen from the results in Table 4, in Comparative Examples 5 to 8 carried out using the positive photosensitive resin composition solution prepared in Comparative Examples 1 to 4, not only the sensitivity was relatively good, but also the 5 wt% weight loss temperature was 460. It can be seen that the heat resistance is not good below the ℃.

Although the embodiment has been described with a line and space (L / S) pattern, the present invention is not limited thereto and the present invention may be applied to miniaturization of various patterns such as hole patterns.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it belongs to the scope of the invention.

1A to 1D are conceptual views for sequentially explaining steps of forming and curing a pattern by applying the photosensitive resin composition for pattern formation of the present invention on a resist semiconductor element.

<Explanation of symbols for the main parts of the drawings>

1: semiconductor device

2: photosensitive resin composition layer

3: exposed part of photosensitive resin composition layer

4: non-exposed part of photosensitive resin composition layer

5: the photosensitive resin composition layer in which the pattern after image development was formed

6: photosensitive resin film after hardening

Claims (9)

(A) a polyamide polymer represented by the following formula (1); (B) esterified quinonediazide compounds; (C) phenol group containing compound; And (D) solvent Positive photosensitive resin composition comprising a. [Formula 1]

(Wherein X ₁ to X ₃ are independently a divalent to tetravalent organic group, Y ₁ to Y ₂ are independently a divalent to hexavalent organic group, E is a residue derived from an aldehyde, R ₁ to R ₂ are each independently hydrogen or an organic group having 1 to 5 carbon atoms, m1 and m2 are each independently 0 to 100 as an average value, m1 + m2 is 5 to 100, n1, n2 and n3 are each independently an integer of 0 to 2, n2 + n3 is an integer of 0 to 3) The method of claim 1, The positive photosensitive resin composition 100 parts by weight of the polyamide polymer; 1 to 50 parts by weight of the esterified quinone diazide compound, based on 100 parts by weight of the polyamide polymer; And 0.1 to 30 parts by weight of the phenol group-containing compound, based on 100 parts by weight of the polyamide polymer, Positive photosensitive resin composition comprising the solvent in the content of 20: 80 to 90: 10 weight ratio with the polyamide polymer. The method of claim 1, The polyamide reacts a dicarboxylic acid monomer and a diamine monomer selected from the group consisting of dicarboxylic acid anhydride, dicarboxylic acid and derivatives thereof, The positive photosensitive resin composition produced by the process of reacting the obtained reaction product with an aldehyde. The method of claim 3, The polyamine monomer is a positive photosensitive resin composition is represented by X (NH ₂ ) ₂ (OH) _{n 1} (X is a divalent to tetravalent organic group, n 1 is an integer of 0 to 2). The method of claim 3, The diamine monomer comprises a silicon-free diamine monomer and a silicon-containing diamine monomer represented by X (NH ₂ ) ₂ (OH) _{n 1} (X is a divalent to tetravalent organic group, n 1 is an integer of 0 to 2). Positive photosensitive resin composition. The method of claim 3, The dicarboxylic acid monomer is Y (COOH) ₂ (COOR) _n2 (OH) _n3 (where n2 is an integer of 0 to 2, n3 is an integer of 0 to 2, R is hydrogen or of 1 to 5 carbon atoms) And an organic group, Y being a divalent to hexavalent organic group). The method of claim 5, Positive type photosensitive resin composition in which X is any one or more of organic groups represented by the following Chemical Formulas 4 to 15. [Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

Wherein A and B are each independently of the other -C-, C (CH ₃ ) _2- , -S-, -O-, -SO _2- , -CO-, -CONH-, C (CF ₃ ) ₂ -Or a single bond) The method of claim 6, Positive type photosensitive resin composition in which Y is any one or more of the organic groups represented by the following formulas (4) to (6) and (11) to (15). [Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

Wherein A and B are each independently of the other -C-, C (CH ₃ ) _2- , -S-, -O-, -SO _2- , -CO-, -CONH-, C (CF ₃ ) ₂ -Or a single bond) The electronic component for semiconductor containing the photosensitive resin film manufactured using the positive photosensitive resin composition of any one of Claims 1-8.

Images