TWI851295B - Developer composition, method of forming pattern, and method of manufacturing semiconductor device - Google Patents

Abstract

The present disclosure provides a developer composition, a method of forming patterns and a method of manufacturing a semiconductor device using the developer composition. The developer composition consists of or includes N,N-diethylformamide.

Description

Developer composition, pattern forming method and method for manufacturing semiconductor device

The present invention relates to a developer composition, a pattern forming method and a method for manufacturing a semiconductor device, and in particular to a developer composition composed of or including N,N-diethylformamide, a pattern forming method using the developer composition and a method for manufacturing a semiconductor device.

With the advancement of semiconductor technology in recent years, the number of transistors placed in integrated circuits has increased, and the technology for miniaturizing chips must be constantly improved. The method of making fine patterns has become an important key.

The developer used to produce fine patterns often uses chemical solvents. As the demand for chips increases, the impact of the use of these chemical solvents on the environment has become difficult to ignore.

Therefore, under the premise of maintaining good developing performance, how to improve the environmental friendliness of the developer, increase the developing rate and reduce the film loss rate are the problems that the technical personnel in this field want to solve.

In view of this, the present invention provides a developer composition, a pattern forming method and a method for manufacturing a semiconductor device, wherein the developing rate can be effectively improved, thereby reducing the film breaking time, while reducing the film loss rate and having a good developing contrast between the exposed area and the non-exposed area, effectively retaining the embossed pattern, and being environmentally friendly.

The present invention provides a developer composition consisting of N,N-diethylformamide.

The present invention provides a developer composition, comprising: N,N-diethylformamide; and a cyclic ketone compound represented by the following formula (1): Formula (1) In formula (1), n is an integer from 1 to 4, wherein the content of N,N-diethylformamide is 35 weight percent or greater based on the total weight of the developer composition and the pH of the developer composition is in the range of 5 to 9.

In one embodiment of the present invention, the developer composition does not substantially contain water.

The present invention provides a developer composition, which is composed of N,N-diethylformamide and a cyclic ketone compound represented by the following formula (1): Formula (1) In formula (1), n is an integer from 1 to 4, wherein the content of N,N-diethylformamide is 35 weight percent or greater based on the total weight of the developer composition and the pH of the developer composition is in the range of 5 to 9.

In one embodiment of the present invention, the developing rate of the developer composition is above 0.6 μm/s.

In one embodiment of the present invention, the film loss rate of the film developed using the developer composition is 20% or less.

In one embodiment of the present invention, the content of N,N-diethylformamide is 55 weight percent or greater.

In one embodiment of the present invention, the content of N,N-diethylformamide is 85 weight percent or greater.

The present invention provides a pattern forming method, comprising: using a photosensitive resin composition to form a photoresist film on a substrate; exposing the photoresist film; and using the developer composition as described above to develop the photoresist film to form a photoresist pattern on the substrate.

In one embodiment of the present invention, the photosensitive resin composition comprises a polyimide precursor having a structural unit represented by the following formula (2): Formula (2) In formula (2), X represents a tetravalent organic group, Y represents a divalent organic group, and _R1 and _R2 each independently represent hydrogen or a monovalent organic group.

In one embodiment of the present invention, X is selected from the group consisting of the following substituents: Wherein R ₃ each independently represents hydrogen, an alkyl group containing 1 to 10 carbon atoms, an alkenyl group containing 2 to 10 carbon atoms, or an alkynyl group containing 2 to 10 carbon atoms, and * is a bond point.

In one embodiment of the present invention, Y is selected from the group consisting of the following substituents: Wherein R ₃ each independently represents hydrogen, an alkyl group containing 1 to 10 carbon atoms, an alkenyl group containing 2 to 10 carbon atoms, or an alkynyl group containing 2 to 10 carbon atoms, and * is a bond point.

In one embodiment of the present invention, at least one of _R1 and _R2 is represented by the following formula (3): Formula (3) wherein R ₄ , R ₅ , and R ₆ are each independently hydrogen or an alkyl group containing 1 to 3 carbon atoms, Z is a divalent organic group, and * is a bonding point.

The present invention provides a method for manufacturing a semiconductor device, comprising: forming a photoresist film on a substrate using a photosensitive resin composition; placing a photomask above the photoresist film to expose the portion of the photoresist film not shielded by the photomask; developing the photoresist film using the developer composition as described above to form a convex photoresist pattern on the substrate; and heating the photoresist pattern to harden the photoresist pattern.

In one embodiment of the present invention, the method for manufacturing a semiconductor device further includes baking the photoresist film after exposing the portion of the photoresist film that is not shielded by the photomask.

In one embodiment of the present invention, the method of developing the photoresist film includes spray development or puddle development.

In one embodiment of the present invention, the method for manufacturing a semiconductor device further includes heating the photoresist pattern to level the photoresist pattern after developing the photoresist film.

Based on the above, the present invention provides a developer composition comprising N,N-diethylformamide or composed of N,N-diethylformamide, a pattern forming method using the developer composition, and a method for manufacturing a semiconductor device, wherein the developing rate can be effectively improved and the film breaking time can be reduced, while having a low film loss rate and being environmentally friendly.

Hereinafter, the exemplary embodiments of the present invention will be described in detail. The present invention is not limited to the exemplary embodiments, and can be implemented in various ways within the scope of the gist thereof. In this specification, the upper limit and lower limit of each numerical range can be arbitrarily combined. < Developer composition >

In the exemplary embodiment, the developer composition is composed of N,N-diethylformamide. In other words, the developer composition of this embodiment includes only N,N-diethylformamide as a single component and no other components. The inventors of the present invention surprisingly found that when N,N-diethylformamide is used alone as a developer composition to develop a film formed by a photosensitive resin, the development rate is significantly improved, the development time (film breaking time) for the pattern to begin to appear is shortened, and there is a lower film loss rate.

In this specification, the development rate is a value calculated by developing the unexposed portion of a film formed of a photosensitive resin using a developer composition according to the following formula: Development rate = thickness difference before and after development of the unexposed portion / development time.

In an exemplary embodiment, the development rate of the developer composition consisting of N,N-diethylformamide may be 0.6 μm/s or greater, for example, 0.7 μm/s or greater, 0.8 μm/s or greater, 0.9 μm/s or greater, 1.0 μm/s or greater, 1.1 μm/s or greater, 1.2 μm/s or greater, 1.3 μm/s or greater, 1.4 μm/s or greater, 1.5 μm/s or greater.

In this specification, the film loss rate is a property calculated by developing the exposed portion of a film formed by a photosensitive resin using a developer composition and using the following formula: Film loss rate = thickness difference of the exposed portion before and after development / thickness of the exposed portion before development * 100%.

In exemplary embodiments, the film loss rate of the developer composition composed of N,N-diethylformamide may be 25% or less, 20% or less, 19% or less, 18% or less, 17% or less, 16% or less, 15% or less, 14% or less, 13% or less, 12% or less, 11% or less, 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, 1% or less, or 1%. Preferably, the film loss rate of the developer composition composed of N,N-diethylformamide may be 20% or less. More preferably, the film loss rate of the developer composition composed of N,N-diethylformamide may be 15% or less. Most preferably, the film loss rate of the developer composition composed of N,N-diethylformamide may be 0% because the difference in the thickness of the developed film is within the measurement error range (±0.1 μm).

In the exemplary embodiment, the developer composition includes N,N-diethylformamide and a cyclic ketone compound represented by the following formula (1): Formula (1) In formula (1), n is an integer from 1 to 4, for example, 1, 2, 3 or 4.

In the exemplary embodiment, the pH of the developer composition is in the range of 5 to 9, such as pH 5 or greater, pH 6 or greater, pH 8 or less, or pH 9 or less. Since the pH of the developer composition of the present invention is in the range of 5 to 9, it is more environmentally friendly than the traditionally used strong alkaline developers.

In the exemplary embodiment, based on the total weight of the developer composition, the content of N,N-diethylformamide may be 35 weight percent or more, preferably, 55 weight percent or more, and more preferably, 85 weight percent or more. For example, based on the total weight of the developer composition, the content of N,N-diethylformamide may be 60 weight percent or more, 70 weight percent or more, 80 weight percent or more.

In the exemplary embodiment, the content of the cyclic ketone compound represented by formula (1) may be 65 weight percent or less, preferably 45 weight percent or less, and more preferably 15 weight percent or less, based on the total weight of the developer composition. For example, the content of the cyclic ketone compound represented by formula (1) may be 60 weight percent or less, 50 weight percent or less, 40 weight percent or less, 30 weight percent or less, 20 weight percent or less, or 10 weight percent or less, based on the total weight of the developer composition.

In an exemplary embodiment, the developer composition may consist only of N,N-diethylformamide and the cyclic ketone compound represented by formula (1) without any other additives.

In the exemplary embodiment, the developer of the present invention may further include other additives without affecting the efficacy. Exemplary additives include, but are not limited to, corrosion inhibitors, surfactants, solvents, etc.

In the exemplary embodiment, the developer composition may not substantially contain water. In this specification, "not substantially containing water" means that the developer composition does not contain additional water, but does not specifically exclude the moisture contained in the raw materials of the developer composition or the moisture caused by the environment. For example, the water content may be less than 0.1 weight percent, such as 0.01 weight percent, based on the total weight of the developer composition.

The developer composition of the present invention comprises N,N-diethylformamide and the cyclic ketone compound represented by formula (1) at the same time, so that when developing, the developing rate is significantly improved, the developing time (film breaking time) for the pattern to begin to appear is shortened, and there is a lower film loss rate.

In exemplary embodiments, the developer composition may have a development rate of 0.6 μm/s or greater, for example, 0.7 μm/s or greater, 0.8 μm/s or greater, 0.9 μm/s or greater, 1.0 μm/s or greater, 1.1 μm/s or greater, 1.2 μm/s or greater, 1.3 μm/s or greater, 1.4 μm/s or greater, 1.5 μm/s or greater.

In exemplary embodiments, the film loss rate of the developer composition may be 25% or less, 20% or less, 19% or less, 18% or less, 17% or less, 16% or less, 15% or less, 14% or less, 13% or less, 12% or less, 11% or less, 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, 1% or less. Preferably, the film loss rate of the developer composition may be 20% or less. More preferably, the film loss rate of the developer composition may be 15% or less. < Pattern forming method and semiconductor device manufacturing method >

In an exemplary embodiment, a pattern forming method for manufacturing a semiconductor device is provided, comprising: forming a photoresist film on a substrate using a photosensitive resin composition; exposing the photoresist film; and developing the photoresist film using the developer composition of the present invention to form a photoresist pattern on the substrate.

In the exemplary embodiment, the method of forming the photoresist film on the substrate is not particularly limited. For example, the photosensitive resin composition is applied to the substrate by a coating method such as spin coating, spray coating, or roller coating.

In the exemplary embodiment, the substrate is not particularly limited, and may be, for example, a glass substrate, a silicon wafer substrate, a ceramic substrate, or a quartz substrate.

In an exemplary embodiment, the photosensitive resin composition may include a polyimide precursor, a photopolymerization initiator, and a (meth) acrylate compound .

In an exemplary embodiment, the polyimide precursor has a structural unit represented by the following formula (2): Formula (2) In formula (2), X represents a tetravalent organic group, Y represents a divalent organic group, and _R1 and _R2 each independently represent hydrogen or a monovalent organic group.

In exemplary embodiments, X is selected from the group consisting of the following substituents: Wherein R ₃ each independently represents hydrogen, an alkyl group containing 1 to 10 carbon atoms, an alkenyl group containing 2 to 10 carbon atoms, or an alkynyl group containing 2 to 10 carbon atoms, and * is a bond point.

In exemplary embodiments, Y is selected from the group consisting of the following substituents: Wherein R ₃ each independently represents hydrogen, an alkyl group containing 1 to 10 carbon atoms, an alkenyl group containing 2 to 10 carbon atoms, or an alkynyl group containing 2 to 10 carbon atoms, and * is a bond point.

As the monovalent organic group of _R1 and _R2 in formula (2), there can be exemplified an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and may also contain an ester bond, an ether bond, a carbonyl bond, an amide bond, a carbamate bond, etc. In addition, the monovalent organic group may have a substituent, and as the substituent, there can be exemplified a halogen atom, a hydroxyl group, an alkoxy group, etc.

In the exemplary embodiment, at least one of _R1 and _R2 is represented by the following formula (3): Formula (3) wherein R ₄ , R ₅ , and R ₆ are each independently hydrogen or an alkyl group containing 1 to 3 carbon atoms, Z is a divalent organic group, and * is a bonding point.

The divalent organic group Z in formula (3) may be an alkylene group or an arylene group, such as but not limited to a methylene group, an ethylene group or a propylene group. In addition, one or more _-CH2- in the above divalent organic group may be replaced by -O- or -COO-.

In the present specification, the alkyl group may be, for example but not limited to, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl or pentyl.

In the present specification, the alkenyl group may be, for example but not limited to, ethenyl, propenyl, isopropenyl, butenyl or pentenyl.

In the present specification, the alkynyl group may be, for example, but not limited to, ethynyl, propynyl, butynyl or pentynyl. Photopolymerization Initiator

In the exemplary embodiment, the photopolymerization initiator is not particularly limited. Suitable photopolymerization initiators include, for example, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, Irgacure OXE03 (BASF Japan Co., Ltd.), TR-PBG3057 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd., trade name), TR-PBG3009 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd., trade name), TR-PBG363 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd., trade name), TR-PBG314 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd., trade name), TR-PBG326 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd., trade name), TR-PBG346 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd., trade name), TR-PBG358 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd., trade name) and other oximes. However, the present invention is not limited thereto.

The photopolymerization initiator may be used alone or in combination of two or more.

In the photosensitive resin composition of the present invention, based on 100 parts by weight of the polyimide precursor, 0.1 to 20 parts by weight of the photopolymerization initiator may be included, preferably 0.5 to 10 parts by weight of the photopolymerization initiator. ( Meth ) acrylate compound

In this specification, "(meth)acrylate" means "acrylate" and/or "methacrylate".

In the photosensitive resin composition of the present invention, the applicable (meth)acrylate compounds are not particularly limited, as long as they are small molecular compounds containing a (meth)acrylate structure. For example, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, 1,6-hexanediol (meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 3-methylpentanediol di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc. can be listed.

The (meth)acrylate compounds may be used alone or in combination of two or more.

In the photosensitive resin composition of the present invention, based on 100 parts by mass of the polyimide precursor, 0.1 to 30 parts by mass of the (meth)acrylate compound may be included, preferably 5 to 20 parts by mass of the (meth)acrylate compound.

In addition to the polyimide precursor, the photopolymerization initiator and the (meth)acrylate compound, the photosensitive resin composition of the present invention may also include other components, such as a sensitizer, a photopolymerizable unsaturated monomer, a thermal polymerization inhibitor, etc.

In an exemplary embodiment, the photoresist film is a negative photoresist formed of a photosensitive resin composition.

The specific step of exposing the photoresist film includes placing a photomask with a pattern above the photoresist film so that light emitted by a light source passes through the photomask to expose the portion of the photoresist film that is not shielded by the photomask.

The wavelength of exposure can be g-line (436 nm) produced by a mercury lamp, h-line (405 nm) produced by a mercury lamp, i-line (365 nm) produced by a mercury lamp, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F2 excimer laser light (157 nm), or X-rays.

The exposure dose may be 1 mJ/cm2 to 520 mJ/cm2. Preferably, the exposure dose may be 280 mJ/cm2 to 520 mJ/cm2. More preferably, the exposure dose may be 320 mJ/cm2 to 500 mJ/cm2.

After exposing the portion of the photoresist film not shielded by the photomask, the photoresist film may be further baked and then developed using a developer composition.

The method of developing the photoresist film using the developer composition is not particularly limited. For example, spray development and/or puddle development may be used for development.

In the exemplary embodiment, the photoresist film is a negative photoresist. Therefore, after the photoresist film is exposed, the unexposed portion of the photoresist film will be dissolved in the developer during development, so that a convex photoresist pattern is formed on the substrate after development.

After the photoresist pattern is formed, the photoresist pattern may be further heated to harden the photoresist pattern.

After the photoresist pattern is formed, a cleaning step may be further performed to remove the developer adhering to the substrate and the photoresist pattern.

After developing the photoresist film, the photoresist pattern may also be heated to level the photoresist pattern.

The following experimental examples are given to more specifically describe the present invention. Although the following experimental examples are described, the materials used, their amounts and ratios, processing details, and processing procedures, etc. may be appropriately changed without exceeding the scope of the present invention. Therefore, the present invention should not be construed restrictively based on the experimental examples described below. < Preparation and Evaluation Results of Developer Compositions > a. Preparation of Developer Compositions 1-9

300 g of cyclopentanone (CPO) and 200 g of N,N-diethylformamide were mixed with a mechanical stirrer to obtain a developer composition 1. Developer compositions 2 to 9 were prepared in the same manner as developer composition 1 according to the ratios shown in Table 1.

Table 1 Developer composition 1 2 3 4 5 6 7 8 9 CPO (g) 300 250 150 100 50 0 500 350 - DEF (g) 200 250 350 400 450 500 0 150 - NMP (g) - - - - - - - - 500 CPO: Cyclopentanone DEF: N,N-diethylformamide NMP: N-methyl-2-pyrrolidone b. Preparation of polyimide precursor b-1 Preparation of polyimide precursor 1

11.99 g of PMDA was placed in a reaction bottle, and 28.63 g of hydroxyethyl methacrylate (HEMA), 18.27 g of pyridine, and 0.13 g of hydroquinone monomethyl ether (MEHQ) were added. γ-Butyrolactone (GBL) was used as a solvent to prepare a solution with a weight percentage concentration of 30%. The solution was heated to 60 °C and reacted for 4 hours under oxygen flow. After the reaction was completed, the temperature was lowered to -15 °C, and 14.72 g of thionyl chloride was slowly dripped in for 2 hours. Separately, 12.42 g of 4,4'-diamino-2,2'-dimethylbiphenyl was mixed with 138.09 g of NMP, and dry nitrogen was introduced. The anhydride solution was pumped into the diamine solution, and the temperature was controlled between -5°C and 0°C. After reacting for about two hours, about 2.38 g of methyl maleic anhydride (m-MAH) was introduced, and the reaction was stirred at room temperature overnight. The precipitate was then filtered to obtain a reaction solution of polyimide precursor 1. b-2 Preparation of polyimide precursor 2

17.06 g of 4,4'-oxydiphthalic anhydride (ODPA) was placed in a reaction bottle, and 28.63 g of hydroxyethyl methacrylate (HEMA), 18.27 g of pyridine, and 0.13 g of hydroquinone monomethyl ether (MEHQ) were added, and γ-butyrolactone (GBL) was used as a solvent to prepare a solution with a weight percentage concentration of 30%. The solution was heated to 60°C and reacted for 4 hours under oxygen flow. After the reaction was completed, the temperature was lowered to 5-10°C, and 13.8 g of N,N'-diisopropylcarbodiimide (DIC) was slowly dripped in, and the reaction was allowed to proceed for 10 minutes. 11.71 g of 4,4'-diaminodiphenyl ether (ODA) was mixed with GBL and dropped into the anhydride solution. After reacting for 12 hours, about 2.38 g of maleic anhydride was introduced and stirred for 1 hour to terminate the reaction. The precipitate was then filtered to obtain a reaction solution of polyimide precursor 2. c. Preparation of photosensitive resin composition c-1. Preparation of photosensitive resin composition 1

100 parts by weight of the polyimide precursor 1 prepared above, 20 parts by weight of triethylene glycol di(meth)acrylate and 3 parts by weight of Irgacure OXE03 (BASF Japan Ltd.) were mixed to obtain a photosensitive resin composition 1. c-2. Preparation of photosensitive resin composition 2

100 parts by weight of the polyimide precursor 2 prepared as above, 20 parts by weight of triethylene glycol di(meth)acrylate and 3 parts by weight of Irgacure OXE03 were mixed to obtain a photosensitive resin composition 2. d. Evaluation method 1. Development rate 1.1 Development rate of photosensitive resin composition 1

The photosensitive resin composition 1 prepared as above was applied to a silicon substrate by a spin coating method to form a coating film with a thickness of about 18 μm. After the coating film was left at room temperature for 10 minutes, it was placed on a heating plate and baked at 100°C for 5 minutes until the coating surface was fixed to form a film for evaluating the development rate. After the film was formed, the initial film thickness was first measured. The film was then developed for 10 seconds with the developer composition 1-9 prepared as above, and then washed with propylene glycol methyl ether acetate (PGMEA) containing 0.55% CPO for 15 seconds, and then dried with an air gun, and the final film thickness was measured. Based on the change in film thickness, the development rate is calculated according to the following formula: Development rate = (initial film thickness - final film thickness) / development time.

The development rate results are shown in Table 2, where the evaluation criteria for the development rate are as follows: A: development rate > 1.2 μm/s; B: development rate 0.6 μm/s ~ 1.2 μm/s; C: development rate < 0.6 μm/s 1.2 For the development rate of the photosensitive resin composition 2

The photosensitive resin composition 2 prepared as above was applied to a silicon substrate by a spin coating method to form a coating film with a thickness of about 30 μm, and then placed on a heating plate and baked at 100° C. for 10 minutes until the coating surface was fixed to form a film for evaluating the development rate. After the film was formed, the initial film thickness was first measured. Then, the film was developed for 10 seconds with the developer composition 1, developer composition 3, developer composition 6, developer composition 7, and developer composition 9 prepared as above, and then washed with propylene glycol methyl ether acetate (PGMEA) containing 0.55% CPO for 15 seconds, and then dried with an air gun, and the final film thickness was measured. The calculation method and evaluation criteria of the development rate of the photosensitive resin composition 2 are the same as those of the photosensitive resin composition 1. The development rate results are shown in Table 2.

Table 2 Photosensitive resin composition 1 Photosensitive resin composition 2 Developer composition 1 2 3 4 5 6 7 8 9 1 3 6 7 9 Development rate B B B B A A C C A B A A C A

The evaluation results of the development rate show that pure N,N-diethylformamide (Developer Composition 6), developer compositions containing N,N-diethylformamide at a content of 35 weight percent or more (Developer Compositions 1-5), and pure N-methyl-2-pyrrolidone (Developer Composition 9) have good development rates for both photosensitive resin compositions. 2. Exposure

The photosensitive resin composition 1 and the photosensitive resin composition 2 prepared as above were coated on a silicon substrate by a spin coating method to form a coating film with a thickness of about 18 μm. After the coating film was left at room temperature for 10 minutes, it was placed on a heating plate and baked at 100° C. for 5 minutes until the coating surface was fixed to form a film for evaluating the exposure amount. Then, the film was exposed by an exposure machine at the exposure energy shown in Table 3 to form a convex cylinder with a diameter of 100 μm and a height of about 18 μm. Next, developer composition 1, developer composition 3, developer composition 6, and developer composition 9 prepared as above were used for two cycles of immersion development, each cycle lasting 15 seconds, and then developed by spraying for 15 seconds. Finally, PGMEA containing 0.55% CPO was used for cleaning for 15 seconds, and then air gun drying was used to observe whether the embossed cylinder with a diameter of 100 μm and a height of about 18 μm could be left. The results are shown in Table 3, where X indicates that it could not be left, and O indicates that it could be left.

Table 3 Photosensitive resin composition 1 Photosensitive resin composition 2 Exposure (mJ/cm ² )/ Developer composition 1 3 6 9 1 3 6 9 280 O O O X O O O X 320 O O O X O O O X 360 O O O X O O O X 400 O O O X O O O X 420 O O O X O O O X 440 O O O X O O O X 460 O O O X O O O X 480 O O O X O O O X 500 O O O X O O O X 520 O O O X O O O X

According to the evaluation results of exposure, it can be seen that when the exposure is in the range of 280mJ/ ^cm2-520mJ / ^cm2 , developer compositions 1, 3, and 6 can leave embossed cylinders. 3. Image integrity

After the film was exposed to 360mJ/ ^cm2 and 460mJ/ ^cm2 exposure to form embossed cylinders, the thickness of the embossed cylinders before and after development with the developer composition 1, developer composition 3, developer composition 6, and developer composition 9 prepared as above was measured, and the film loss rate (Film loss) of the embossed cylinders was calculated according to the following formula. Film loss rate = Thickness difference of embossed cylinders / Thickness of embossed cylinders before development * 100%

The results are shown in Table 4.

Table 4 Photosensitive resin composition 1 Photosensitive resin composition 2 Exposure/Developer Composition 1 3 6 9 1 3 6 9 360mJ/ ^cm2 14.0% 14.0% 0%* 100% 19.1% 20.0% 17.3% 100% 460mJ/ ^cm2 6.7% 8.6% 3.7% 100% 17.0% 15.4% 16.0% 100% *The film thickness after development is within the measurement error range of the film thickness before development (±0.1μm)

From the results in Table 4, it can be seen that the film loss rates of the developer compositions 1, 3, and 6 of the present invention are all below 20.0%. Among them, pure N,N-diethylformamide (developer composition 9) has almost no film loss rate when developing the photosensitive resin composition 1. Therefore, using the developer compositions 1, 3, and 6 for development can achieve a higher image integrity. In contrast, although pure N-methyl-2-pyrrolidone (developer composition 9) has a high development rate for the photosensitive resin composition, its film loss rate is also 100%, and it is not possible to effectively form a photoresist pattern.

In summary, the present invention is a developer composition, a pattern forming method and a method for manufacturing a semiconductor device, wherein the developing rate can be effectively improved, thereby reducing the film breaking time, while reducing the film loss rate and effectively retaining the photoresist pattern, and is environmentally friendly.

Although the present invention has been disclosed as above by the embodiments, they are not intended to limit the present invention. Any person with ordinary knowledge in the relevant technical field can make some changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be defined by the scope of the attached patent application.

without

without

Claims (11)

A pattern forming method comprises: forming a photoresist film on a substrate using a photosensitive resin composition; exposing the photoresist film; and developing the photoresist film using a developer composition to form a photoresist pattern on the substrate, wherein the developer composition comprises: 35 to 100 weight percent of N,N-diethylformamide; and 0 to 65 weight percent of a cyclic ketone compound represented by the following formula (1): Formula (1) In formula (1), n is an integer from 1 to 4, wherein the photosensitive resin composition comprises a polyimide precursor having a structural unit represented by the following formula (2): Formula (2) In formula (2), _R1 and _R2 each independently represent hydrogen or a monovalent organic group, and X is selected from the group consisting of the following substituents: wherein R ₃ each independently represents hydrogen, an alkyl group containing 1 to 10 carbon atoms, an alkenyl group containing 2 to 10 carbon atoms, or an alkynyl group containing 2 to 10 carbon atoms, and * is a bonding point, and Y is selected from the group consisting of the following substituents: Wherein R ₃ each independently represents hydrogen, an alkyl group containing 1 to 10 carbon atoms, an alkenyl group containing 2 to 10 carbon atoms, or an alkynyl group containing 2 to 10 carbon atoms, and * is a bond point. In the pattern forming method according to claim 1, at least one of _R1 and _R2 is represented by the following formula (3): Formula (3) wherein R ₄ , R ₅ , and R ₆ are each independently hydrogen or an alkyl group containing 1 to 3 carbon atoms, Z is a divalent organic group, and * is a bonding point. The pattern forming method as described in any one of claim 1, wherein the development rate of the developer composition is greater than 0.6 μm/s. A pattern forming method as described in any one of claim 1, wherein the film loss rate of the photoresist film after development using the developer composition is 20% or less. The pattern forming method as described in claim 1, wherein the developer composition contains 55 weight percent to 100 weight percent of N,N-diethylformamide. The pattern forming method as described in claim 1, wherein the developer composition contains 85 weight percent to 100 weight percent of N,N-diethylformamide. The pattern forming method as described in claim 1, wherein the developer composition contains 100 weight percent of N,N-diethylformamide. A method for manufacturing a semiconductor device, comprising: forming a convex photoresist pattern on a substrate using a pattern forming method as described in any one of claims 1 to 7; and heating the photoresist pattern to harden the photoresist pattern. The method for manufacturing a semiconductor device as described in claim 8 further includes baking the photoresist film. A method for manufacturing a semiconductor device as described in claim 8, wherein a method for developing the photoresist film includes spray development or puddle development. The method for manufacturing a semiconductor device as described in claim 8 further includes heating the photoresist pattern to level the photoresist pattern after developing the photoresist film.