JP2001056559A - Polyamide polymer containing carbonic ester side chain and heat resistant photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyamide polymer having a low dielectric constant and giving a photoresist composition excellent in heat resistance by incorporating a specified carbonic ester side chain. SOLUTION: The polyamide polymer contains a carbonic ester side chain of formula I, wherein Ar1 is a tetravalent aromatic group selected from groups of formula II, X1 is -CH2-, -O-, -S-, -SO2-, -CO- or the like, Ar2 is a divalent aromatic group selected from groups of formula III, etc., R1 and R2 are each a group of formula IV, R' and R'' are each 1-4C alkyl, phenyl or phenyl substituted by a substituent selected from a nitro group and a halogen and 5<=m+n<=500. The polyamide polymer having the formula I as repeating units is a homo- or copolymer. When the polyamide polymer is mixed with a photo- acid generating agent, it can be utilized as a positive type photosensitive heat resistant low dielectric.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide polymer containing a side chain of a carbonic acid ester and a heat-resistant photoresist composition. More specifically, a portion exposed to light is dissolved by a developing solution to receive the light. The remaining parts are not
Passivation by adding a new polyamide polymer containing a side chain of a carbonate ester having a function capable of being converted into a heat-resistant polymer by a heating step as a post-process, and containing the polyamide polymer and a small amount of a photoacid generator. Membrane (passivation laye
r), a heat-resistant photoresist composition which can be used for a buffer coat or an interlayer insulating film of a multilayer printed circuit board.

[0002]

2. Description of the Related Art Semiconductor passivation films (passivation films)
A heat-resistant material is used to form a layer, a buffer coat or an interlayer insulating film of a composite multilayer printed circuit board. In addition, in order to electrically connect the upper and lower layers or to perform multi-layer wiring, complex flat plate printing such as photoresist coating, prebake, UV exposure, development, etching, film removal, etc. is performed on the thin film of the heat-resistant insulator again. (lith
ography) process.

However, if the thin film material of the heat-resistant insulator keeps the photosensitive group, it is possible to manufacture holes required for electrical connection at the time of performing the film-forming step of the heat-resistant insulating layer without using the above-described photoresist process. And the process is greatly simplified. In addition, productivity can be increased by reducing the amount of resist and chemicals used, shortening the process, and the like. Further, it is possible to prevent the reproducibility and the resolving power of the pattern reproduced from the lithographic printing step from being deteriorated due to the etching step of the heat-resistant insulator. Therefore, the process can be greatly simplified by using a heat-resistant photoresist in which the function of the photoresist and the function of the heat-resistant insulator are combined.

The photoresist is removed by removing the film after a pattern forming process such as exposure, development and etching is completed. However, in the case of a heat-resistant photoresist, since the photoresist is permanently present in the semiconductor element, the photosensitivity, In addition to the characteristics of photosensitive functional materials such as resolution, transparency, developability, insulation, heat resistance,
Properties required for semiconductor and electronic process materials, such as mechanical and low dielectric properties, are also required at the same time. The above-mentioned heat-resistant photoresist can be applied to all fields in which a low-dielectric material in the form of a thin film is used, and is mainly used for a passivation layer and a buffer film of a semiconductor device.
t) Or applied to multilayer printed circuit boards.

Conventional heat-resistant photoresists are disclosed in German Patent No. 2,437,348 or J. Macromolecluar Science A2.
As reported in 1, 1641 (1984) and the like, negative photosensitive polyimides using a photocrosslinkable polyimide precursor having an ester group or an ionic group introduced as a side chain have been mainly developed. However, negative-type heat-resistant photoresists may cause erroneous shapes due to particles or cracks existing on the photomask, and use an organic solvent as a developing solution. It can happen.

On the other hand, US Pat. No. 4,927,736 discloses a positive-type photosensitive heat-resistant photoresist in which a photosensitive agent such as naphtoquinone diazide (hereinafter, referred to as “NQ”) is substituted with an aromatic polyimide containing a hydroxy group. It reported that the compound was organically bonded or mixed. A large amount of a photosensitizer must be used for an aromatic polyimide containing a hydroxy group, since the light absorption is large and the quantum yield is eventually low. But,
In the process of converting the unexposed portion to a heat-resistant polymer by heating, the polar pyrolysis products of the photosensitizer used are large in the film, and a polar group (e.g., -OH group) is further present in the main chain of the polymer. Since it remains as it is, a high dielectric constant causes a decrease in heat resistance.

As another example, in order to improve photosensitivity and resolution, a chemically amplified acid-sensitive group is substituted with an aromatic polyimide containing a hydroxy group [Polymers for Advanced Tech.
nology, vol. 4, 277, 287, 1992] or amic acid t
Introduced into ert-butyl ester polyimide precursor [European Patent Publication No. 0502400A1] to block -OH or -COOH to lower the solubility in basic aqueous solution as a developer, and after photoreaction of photoacid generator The generated acid decomposes the acid-sensitive group, regenerates —OH or —COOH, and solubilizes the developer. However, in this case, a chemically amplified photosensitive effect that increases the quantum efficiency can be obtained.In the former case, however, the acid-sensitive group is generated by decomposition of the acid-sensitive group from the final heat treatment process. There is a disadvantage that remains in the film. In European Patent Publication No. 0502400A1,
Since the amount of the photoacid generator used as a mixture is extremely large, the dielectric constant is increased and the heat resistance is deteriorated.

On the other hand, US Pat. Nos. 5,449,584 and 5,037,7
According to No. 20, a polyamide polymer containing a hydroxy group capable of being thermally converted to polybenzoxazole was mixed or organically bonded with a photosensitive group. Since the photosensitive group used at this time does not use a chemically amplified sensitizer as a derivative of naphthoquinonediazide (NQ), a large amount of sensitizer must be used. Also, in the process of converting the unexposed part of the precursor into a heat-resistant polymer, a large amount of polar pyrolysis products of the used photosensitizer are present in the film, causing the dielectric constant to increase and the mechanical properties to deteriorate. become.

[0009]

As a part of such research, the present inventors have proposed to increase the dielectric constant due to -OH generated after heat treatment, which was a disadvantage of the existing photosensitive heat-resistant photoresist, and to increase the heat resistance. Research has been devoted to ways to fundamentally improve problems such as reduced photosensitivity and enhance photosensitivity. As a result, a new positive type that combines both chemically amplified photosensitization technology that ensures a high quantum yield and technology that minimizes the use of photosensitizers and removes unreacted polar groups, which is the cause of increasing the dielectric constant. The present invention was completed by completing the heat resistant and low dielectric technology.

Therefore, in the present invention, by heating a patterned non-exposed portion, a hydroxy group formed by thermal decomposition of a carbonate ester side chain is induced to a heat-resistant reaction, thereby being the most thermally stable. A novel carbonate polymer containing a carbonic ester side chain, which is highly molecularly designed to prevent the increase of the dielectric constant due to the remaining hydroxy group by converting to a benzoxazole group, and to maintain high heat resistance. Has its purpose in providing

It is another object of the present invention to provide a novel heat-resistant photoresist composition having a low dielectric constant by incorporating a minimum amount of a photoacid generator into the polyamide polymer.

[0012]

The present invention is characterized by a polyamide polymer containing a carbonate side chain represented by the following chemical formula 1.

[0013]

Embedded image Represents phenyl which is substituted by a substituent selected from nitro and halogen atom; m + n is in the range of 5 to 500; the combination of the above-mentioned Ar ₁ and Ar _2, Formula 1
Is a homopolymer or a copolymer.

The present invention will be described in more detail as follows. As shown in the above Chemical Formula 1, the polyamide polymer containing a carbonate side chain according to the present invention may have an alkyloxycarbonyloxy group (-OH or an acid sensitive group).
It has the structure of a polyamide polymer synthesized from a tetravalent compound of an aromatic diamine containing OCOOR) and a dicarboxylic acid and its derivative. Due to this molecular structural specificity, the polyamide polymer of the present invention can be used as a positive-type photosensitive heat-resistant low dielectric substance by mixing with a photoacid generator. That is, after applying a heat-resistant photoresist composition obtained by mixing a polyamide polymer and a photoacid generator in a thin film on a substrate, and exposing through a photomask engraved with a pattern with visible light or ultraviolet light, In the part, the side chain of the alkyloxycarbonyloxy group (-OCOOR), which is an acid-sensitive group, is converted to a hydroxy group (-OH) by a thermal decomposition reaction and tetramethylammonium hydroxide
de, hereinafter referred to as “TMAH”). On the other hand, the non-exposed portion, which has not received light, has a low solubility in the basic aqueous solution, so that a positive pattern of the polyamide polymer can be formed. By heating the non-exposed portion thus patterned, a hydroxy group (-OH) is generated by a thermal decomposition reaction of an alkyloxycarbonyloxy group (-OCOOR), which is an acid-sensitive group in the polyamide polymer, When heated at a higher temperature, -OH bonds to a carbonyl group, which is an adjacent reactive group, and can be converted to a benzoxazole group, which is a low-dielectric group having excellent heat resistance. The above polybenzoxazole has extremely excellent heat resistance and shows heat resistance of 500 ° C. or more,
Not only is it a very stable substance that has almost no organic solvent to dissolve it, but also has a lower dielectric constant and absorptivity than ordinary polyimide. -OCOOR used as an acid-sensitive group
Is a chemical that is decomposed and has a volatile low molecular weight (e.g.,
(Isobutene, styrene or its derivatives) and gasified to CO ₂ and no decomposed substances remain inside the film, so photosensitive polyimide (PSPI) or tert-butoxy group using naphthoquinonediazide (NQ) (Hereinafter “t-boc”
) Shows a much lower dielectric constant than using a polyimide having a side chain of That is, not only is -OH, which is a cause of inferior low dielectric properties, heat resistance properties, and electrical properties, removed in the polymer, but it is also applied to the heat resistance reaction. In addition, since a photoacid generator and an acid-sensitive group are used as a concept of the chemical amplification type, a large amount of acid is generated when decomposed by light or an acid to accelerate the decomposition of the acid-sensitive group.
Accordingly, since the quantum efficiency is high, the amount of the photoacid generator used can be minimized, and an increase in the dielectric constant and a decrease in various physical properties due to the photoacid generator can be minimized.

Generally, polyimide and polybenzoxazole have large light absorption in the visible light and ultraviolet regions, and the color of the film shows a color from yellow to brown, so that a considerable amount of ultraviolet light is absorbed and the quantum yield is low. Tends to decrease. On the other hand, the polyamide polymer according to the present invention can exhibit higher photosensitivity since a colorless and transparent polymer is obtained as a polyamide polymer immediately after coating.

The concentration [n / (m + n)] of the acid-sensitive group (—OCOOR) contained in the polyamide polymer according to the present invention is 1 to 90.
%, Preferably in the range of 3 to 70%. The acid-sensitive group (-O
If the concentration of (COOR) is excessively high, the developing speed decreases, and a long exposure time or a large amount of a photoacid generator is required. However, if the concentration of the acid-sensitive group (-OCOOR) is extremely low, there is a possibility that the resolution may be insufficient and the thickness may be reduced. The degree of polymerization (m + n) indicating the molecular weight of the polyamide polymer according to the present invention is in the range of 5 to 500.

Further, the polyamide polymer having the repeating unit of the above formula 1 includes all homopolymers and copolymers composed of a combination of Ar ₁ and Ar ₂ .

As described above, the polyamide polymer of the present invention is produced from an aromatic diamine having a dihydroxy group and an aromatic dicarboxylic acid or a derivative thereof. It is on the street. Reaction formula 1 In the above reaction formula, Ar ₁ , Ar ₂ and R are each the same as defined above; X represents —OH, a halogen atom, an alkoxy group or a phenoxy group.

As the polymerization method of the polyamide polymer according to the above reaction formula 1, polymerization by acid chloride, polymerization using silyl chloride, ester substitution reaction, direct polymerization, or the like is possible. The molecular weight of the polyamide polymer ranges from 0.1 to 2.5 dL / g as the intrinsic viscosity. The polymerization reaction temperature is maintained at a low temperature of 50 ° C or lower, preferably 30 ° C or lower. If the polymerization reaction temperature is extremely high, an excessive reaction occurs to easily generate polybenzoxazole which is insoluble in a solvent, and a polymer having a low molecular weight is formed.

As a method for bonding an alkyloxycarbonyloxy group (—OCOOR), which is an acid-sensitive group, to a polymer, an acid anhydride or chloride containing an alkyloxycarbonyloxy group is excessively used to prepare a basic solution. Reaction within. According to the present invention, examples of the reaction catalyst include basic substances such as pyridine, potassium tert-butoxide, triethylamine, dimethylaminopyridine, 1,4-diazabicyclo [2,2,2] octane and the like. It is desirable that the reaction for introducing the acid-sensitive group be carried out at room temperature or below, if possible. If the reaction temperature is high, the thermal decomposition reaction of the acid-sensitive group and the formation of polybenzoxazole may occur.

On the other hand, the present invention includes a heat-resistant photoresist composition obtained by including a polyamide polymer represented by the above formula 1 and a photoacid generator.

As the photoacid generator contained in the heat-resistant photoresist composition according to the present invention, various photoacid generators known in the literature as substances which generate an acid upon exposure can be used. Desirably, a substance that absorbs light in an absorption region (300 nm or more) longer than the absorption region of the polyamide polymer used at the same time to generate an acid is used. The following is a specific example of the photoacid generator. However, the photoacid generator of the present invention is not limited to the substances exemplified below.

[0023]

Embedded image

In the above compound, R ₃ , R ₄ , R ₈ , R ₁₀ , R ₁₁ and
R ₁₂ are each an alkoxy group of which a hydrogen atom or a C ₁ -C _10, specifically, a hydrogen atom, a methoxy group, an ethoxy group, a propoxy group, a butoxy group; R ₅ is C ₁ ~
Alkyl C _10, haloalkyl group of C ₁ -C _10, a substituted or unsubstituted phenyl group or Kamuhoruniru group with an alkyl group, specifically, an ethyl group, an ethyl group, a trifluoromethyl group, a phenyl group, 4-methylphenyl group,
R ₆ , R ₇ and R ₉ represent a hydrogen atom,
A halogen atom, an alkyl group of C ₁ -C _10, shown specifically, a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom, a methyl group, an ethyl group, a propyl group or a butyl group.

The above-mentioned photoacid generator is contained as 0.3 to 20% by weight based on the polyamide polymer. Excessive use of the photoacid generator not only deteriorates the dielectric properties, mechanical strength, and heat resistance in the film, but also impairs the light transmittance, making it difficult to form a complete hole. However, if the amount used is extremely small, sufficient acid will not be present and the role as an acid generator will not be sufficiently exhibited, resulting in poor resolution.

The heat-resistant photoresist composition according to the present invention can be manufactured and used in the form of a solution. Examples of the solvent include dimethyl sulfoxide, hexamethylphosphamide, dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, gamma-butyrolactone, diglyme (diglyme), butoxyethanol, propylene glycol methyl ethyl acetate (PGMEA), and the like. But not limited to a particular solvent. However, it is preferable to use an ester or ether solvent rather than an amide solvent. In addition, two or more solvents can be used as a mixture of the above solvents in order to control the uniformity and thickness of the thin film and to improve the adhesive strength. The heat-resistant photoresist composition is prepared so that its concentration is in the range of 0.1 to 70% by weight, and is used after being adjusted according to the thickness of the coating.

The formation of a thin film using a heat-resistant photoresist composition can be performed by any of spin coating, bar coating and doctor blade methods widely used in the electronics industry. The drying temperature for forming a thin film is suitably from 40 to 150 ° C. If the drying temperature is extremely low, the drying time is prolonged. If the drying temperature is extremely high, the color is converted into a dark color by the thermal decomposition of the acid-sensitive group and the formation of benzoxazole, so that the transmittance decreases.

Exposure may be performed using an exposure apparatus that exhibits visible light or ultraviolet light having a wavelength of 200 to 500 nm, and it is desirable to use an exposure device equipped with a filter that exhibits a monochromatic wavelength. More advantageous in aspects. The invention is not limited to any particular equipment or exposure equipment.

The exposure time can be changed according to the experimental conditions. According to the present invention, when using an ultraviolet exposure apparatus equipped with a used 365 nm filter, the exposure time is 15 to 110
The exposure time can be reduced to seconds, and the exposure time can be shortened by a more powerful exposure apparatus. The exposure energy is quantified by an energy meter, and the resolving power is confirmed by depth and width by a profile meter. The cross section of the thin film is confirmed by an electron microscope. The present invention will be described in more detail based on the following examples, but the present invention is not limited thereto. Example 1 Pyridine (20%) was placed in a 500 mL flask under a nitrogen atmosphere.
ml), 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (30 g, 0.082 mol) and isophthalic dichloride (16.62 g, 0.082 mol) were added and stirred. After dissolution, the reaction was allowed to proceed for 12 hours while maintaining 0 ° C. The obtained viscous liquid is
Precipitated in methanol solution (1 L) cooled to 0 ° C and 50 ° C
Dried in a vacuum oven. After dissolving the obtained white precursor powder again in tetrahydrofuran (THF), while dissolving 4 equivalents of di-tert-butyl dicarbonate (71.5 g) in pyridine (0.5 g) as a basic catalyst, 12 Stir again over time. The resulting viscous liquid was precipitated in a methanol solution cooled to 0 ° C., filtered, washed and dried several times with methanol and water to obtain a powder of a polyamide polymer to which an acid-sensitive group was bonded. The intrinsic viscosity of the obtained polymer was 0.70 dL / g.

According to the contents shown in the following Table 1, the polyamide polymer obtained above (intrinsic viscosity: 0.70 dL / g) and p-nitrobenzyl-9,10-dimethoxyanthracene-2- as a photoacid generator were used. Gamma-butyrolactone (1
(50 ml) and filtered through a 0.25 μm filter. The above solution was spin-coated on a silicon wafer, and accelerated dried at 110 ° C. for 5 minutes to obtain a thin insulator film having a thickness of 12 μm. Exposure was performed for 45 seconds through a photomask using an ultraviolet exposure apparatus equipped with a 365 nm filter. Then, after heating at 110 ℃ for 5 minutes, it is a developer
2.38 wt% tetramethylammonium hydroxide (TMAH)
And washed with water. The wafer on which this pattern was formed was heated in an oven at 350 ° C. to obtain a cured pattern. Regarding the resolving power, the depth and width were confirmed with a profile instrument, and the cross section of the thin film was observed with an electron microscope. The results are shown in Table 1 below.

[0031]

[Table 1] Table 1

Example 2 In the same manner as in Example 1 above, the polymerization reaction temperature was raised to 50 ° C. to obtain a polyamide polymer having an intrinsic viscosity of 0.25 dL / g. A method similar to that of Example 1 above, using the synthesized polyamide polymer and 3% by weight of p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (NBAS) as a photoacid generator. Dissolved, coated, dried, exposed, developed and cured. The results are shown in Table 2 below.

[0033]

[Table 2] Table 2

Example 3 A polyamide polymer was produced in the same manner as in Example 1 except that the amount of di-tert-butyl dicarbonate added was 0.5 equivalent, 2 equivalent, 10 equivalent, and 20 equivalent, respectively. The concentration of t-boc, an acid-sensitive group, was adjusted by changing to a double equivalent. Example 1 was prepared using the synthesized polyamide polymer and 3% by weight of p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (NBAS) as a photoacid generator.
Dissolve, coat, dry, develop and cure in the same manner as in, with exposure times of 15 seconds, 25 seconds, 70 seconds,
110 seconds. The results are shown in Table 3 below.

[0035]

[Table 3] Table 3

Example 4 Pyridine (6) was placed in a 300 mL flask under a nitrogen atmosphere.
ml), 3,3'-diamino-4,4'-dihydroxybiphenyl (10
g, 0.046 mol) and isophthalic dichloride (9.4 g, 0.46 mol)
Was stirred and dissolved in dimethylformamide, and the reaction was allowed to proceed for 12 hours while maintaining 0 ° C. The obtained viscous liquid was precipitated in a methanol solution (1 L) cooled to 0 ° C., and dried in a vacuum oven at 50 ° C. After dissolving the obtained pale yellow precursor powder again in tetrahydrofuran (THF), a 4-fold equivalent of di-tert-butyl dicarbonate was dissolved in potassium-t-butoxide (0.4 g) as a basic catalyst. While stirring again for 12 hours. The obtained viscous liquid was precipitated in a methanol solution cooled to 0 ° C., filtered, washed and dried several times with methanol and water to obtain a powder of a polyamide polymer having an acid-sensitive group bonded thereto. The intrinsic viscosity of the obtained polymer is 0.52 dL
/ g.

The same procedure as in Example 1 was carried out except that the synthesized polyamide polymer and 3% by weight of p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (NBAS) were used as a photoacid generator. Dissolution, coating, drying, development and curing were performed by various methods, and the exposure time was 75 seconds. The results are shown in Table 4 below.

[0038]

[Table 4] Table 4

Example 5 Under a nitrogen atmosphere, triethylamine (5 ml), 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (10 g, 0.0273 mol) and oxy-
Di-benzoic acid chloride (8.0 g, 0.0273 mol) was added and stirred,
After dissolving in dimethylformamide, the reaction was allowed to proceed for 12 hours while maintaining 0 ° C. The obtained viscous liquid was precipitated in a methanol solution (1 L) cooled to 0 ° C., and dried in a 50 ° C. vacuum oven. After dissolving the obtained white precursor powder again in tetrahydrofuran (THF), while dissolving 4 equivalents of di-tert-butyl dicarbonate in pyridine (0.5 g) as a basic catalyst, again over 12 hours. It was allowed to stir. The obtained viscous liquid was precipitated in a methanol solution cooled to 0 ° C., filtered, washed and dried several times with methanol and water to obtain a powder of a polyamide polymer having an acid-sensitive group bonded thereto. The intrinsic viscosity of the obtained polymer was 0.47 dL / g.

The same procedure as in Example 1 was carried out using the synthesized polyamide polymer and 4% by weight of p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (NBAS) as a photoacid generator. Melted, coated, dried, exposed, developed and cured in a similar manner. The results are shown in Table 5 below.

[0041]

[Table 5] Table 5

Example 6 Under a nitrogen atmosphere, triethylamine (5 ml), 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (10 g, 0.0273 mol) and isophthalic acid Chloride (2.77 g, 0.0136 mol) and oxy-di-benzoic acid chloride (4.0 g, 0.0136 mol) were added and stirred, and dissolved in dimethylformamide.
The reaction was allowed to proceed for 2 hours. The obtained viscous liquid was precipitated in a methanol solution (1 L) cooled to 0 ° C.
Dried in a vacuum oven at ℃. After dissolving the obtained white precursor powder again in tetrahydrofuran (THF), while dissolving 4 equivalents of di-tert-butyl dicarbonate in pyridine (0.5 g) as a basic catalyst, again over 12 hours. Stirred. The obtained viscous liquid was precipitated in a methanol solution cooled to 0 ° C., filtered, washed and dried several times with methanol and water to obtain a powder of a polyamide polymer having an acid-sensitive group bonded thereto. The intrinsic viscosity of the obtained polymer is 0.47
dL / g.

Example 1 was repeated using the synthesized polyamide polymer and 4% by weight of p-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate (NBAS) as a photoacid generator. Melted, coated, dried, exposed, developed and cured in a similar manner. The results are shown in Table 6 below.

[0044]

[Table 6] Table 6

Example 7 The intrinsic viscosity produced by the production method of Example 1 was 0.70
Coating, drying, exposure, development, and curing were performed in the same manner as in Example 1 above, using the polyamide polymer and each of the compounds shown in Table 7 below as a photoacid generator in the dL / g range. The results are shown in Table 7 below.

[0046]

[Table 7]

[0047]

As described above, the polyamide polymer containing a carbonate side chain according to the present invention is bonded as a functionalized polymer capable of inducing a heat-resistant reaction of OH groups, particularly as an acid-sensitive group. since the interior of the gasification has been coating with which -OCOOR as chemicals and CO ₂ having a low molecular weight of the degraded volatile does not remain whatsoever of decomposition products, naphthoquinone diazide which have been used in the usual manner (NQ)
Shows a dielectric constant much lower than that of a heat-resistant photoresist or a polyimide precursor having a tert-butoxy group.

Accordingly, the heat-resistant photoresist composition containing the polyamide polymer and a small amount of the photoacid generator according to the present invention can be used in all fields where low dielectric materials are used, and especially for semiconductor devices. Passivation film (passi
It is useful as a material for a vation layer, a buffer coat or an interlayer insulating film of a composite multilayer printed circuit board.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Choi Ji Yeon ▼ Republic of Korea 431-6, Yuseong-gu, Daejeon Metropolitan City 431-6 Modern Apartment 101 Building No. 904 No. 904 (72) Inventor Yuan Jongsan Korea Daejeon-gu, Daejeon Metropolitan City Uoil-dong 99 Hanbit Apartment 129 Building 801 No. 801 (72) Inventor Kim Tae-yeon 130-17 Songpa-dong, Songpa-gu, Seoul, South Korea (72) Inventor Yu Sae-seon 1334, Seocho-dong, Seocho-gu, Seoul, South Korea Dong-A Apartment 8 Building No. 1008 No. 72 (72) Inventor Park Dong-Dong South Korea Daejeon Metropolitan City Yuseong-gu Tanmin-dong (No address) Seong Apartment 103 Building No. 1504 No. 72 (72) Inventor Wu Jae ▲ Min ▼ South Korea Daejeon Metropolitan City Danmin-dong, Yuseong-gu (No address) Expo Apartment 404 Building 1605 No. (72) Inventor Li Takeei South Korea Hiroshiiki City Yuseong 區 Taminhora (no address) Yoso apartments 111 houses 307 號

Claims (6)

[Claims] 1. A polyamide polymer containing a carbonate side chain represented by the following chemical formula 1. Embedded image Represents phenyl which is substituted by a substituent selected from among Toro and halogen atom; m + n is in the range of 5 to 500; polyamide heavy for the Formula 1 and repeating units by combination of the above-mentioned Ar ₁ and Ar ₂ The coalescence is a homopolymer or a copolymer. 2. The polyamide polymer having a carbonate side chain according to claim 1, wherein the concentration of the acid-sensitive group (—OCOOR) contained in the polyamide polymer is in the range of 3 to 70%. 3. The polyamide polymer has an intrinsic viscosity of 0.1 to less than 0.1.
The polyamide polymer having a side chain of a carbonic ester according to claim 1, wherein the amount is in the range of 2.5 dL / g. 4. A photosensitive heat-resistant photoresist composition comprising a polyamide polymer represented by the following chemical formula 1 and a photoacid generator in an amount of 0.3 to 20% by weight based on the polyamide polymer. object. In the formula, Ar ₁ , Ar ₂ , R, m and n are each as defined in claim 1.
It is the same as that defined in. 5. The heat-resistant substance according to claim 4, wherein the photoacid generator is a substance that generates an acid by absorbing light in a long wavelength region (300 nm or more) in the light absorption region of the polyamide polymer. Photoresist composition. 6. The heat-resistant photoresist composition according to claim 3, wherein said photoacid generator is selected from the following compounds. Embedded image In the above, R ₃ , R ₄ , R ₈ , R ₁₀ , R ₁₁ and R ₁₂ each represent a hydrogen atom or a C _{1 to} C ₁₀ alkoxy group; R ₅ is a C ₁ to C _10
10 alkyl group, a halogenated alkyl group of C ₁ -C _10, a substituted or unsubstituted phenyl group or Kamuhoruniru an alkyl _{group; R 6, R 7, R} 9 is a hydrogen atom, a halogen atom, C ₁ ~ C _{10 represents} an alkyl group.