KR20080099413A - Thinner composition for photosensitive resin removal - Google Patents

Abstract

The present invention (a) alkyl amide represented by the following formula (1); (b) alkyl pyrrolidone represented by the following formula (2); And (c) relates to a thinner composition for removing a photosensitive film resin comprising a fluorinated acrylic copolymer.

<Formula 1>

In Formula 1, R ₁ , R ₂ and R ₃ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, provided that at least one of R ₁ , R ₂ and R ₃ is an alkyl group having 1 to 4 carbon atoms. .

<Formula 2>

In Formula 2, R ₄ and R ₅ are each independently an alkyl group having 1 to 4 carbon atoms unsubstituted or substituted with hydrogen or a hydroxyl group.

Description

Thinner composition for removing photosensitive resin

The present invention relates to a thinner composition for removing a photosensitive resin used in the manufacturing process of a semiconductor device and a flat panel display device. The photolithography process is a process of manufacturing a semiconductor device or a flat panel display device by applying a photosensitive resin composition on a wafer or a substrate, transferring a predesigned pattern, and then performing an etching process appropriately according to the transferred pattern. It is one of the very important tasks to construct the circuit.

The photolithography process includes (1) an application step of uniformly applying the photosensitive resin composition to the surface of the wafer or substrate, and (2) soft baking to evaporate the solvent from the applied photosensitive film so that the photosensitive film adheres to the surface of the wafer or substrate ( a soft baking) process, (3) an exposure process of transferring a mask pattern onto the photoresist by exposing the photoresist while repeatedly reducing the circuit pattern on the mask repeatedly and sequentially using a light source such as ultraviolet light, and (4) a light source. Development process of selectively removing parts with different physical properties such as difference in solubility due to exposure to exposure by using developer, (5) Wafer or substrate after development A hard baking process for more tightly fixing the photoresist film remaining on the wafer or the substrate, (6) an etching process of etching a predetermined portion according to the developed pattern of the photosensitive film, and (7) the process Then, it progresses to the peeling process etc. which remove the photosensitive film which became unnecessary.

In the photolithography process, a photocoating film is supplied onto a wafer or a substrate and the substrate is rotated to spread the surface evenly by centrifugal force. As a result, centrifugal force causes the photoresist film to gather on the edge portion and the rear surface of the substrate to form a small spherical material. . The spherical material may be peeled off during transfer of the substrate after the baking process to cause particles in the apparatus, or may cause defocus during exposure. This unnecessary photosensitive material causes equipment contamination and lowers the yield in the manufacturing process of the semiconductor device or the flat panel display device. Therefore, spray nozzles are installed above and below the edge part and the rear part of the substrate in order to remove them. Thinner (Thinner) composition consisting of an organic solvent component is injected to the edge portion and the rear portion to remove it.

Factors that determine the performance of the thinner composition include dissolution rate and volatility. The dissolution rate of the thinner composition is very important as the ability to dissolve and remove the photosensitive resin quickly and effectively. Specifically, in the rinse of the edge portion, it may have a smooth treatment cross section only if it has an appropriate dissolution rate, and if the dissolution rate is too high, a photoresist attack may appear in the rinse of the photoresist applied to the substrate. On the contrary, when the dissolution rate is too low, a partially dissolved photosensitive film tail flow phenomenon called tailing may appear in the rinse of the photosensitive film applied to the substrate. In particular, in the case of the rinsing process using a rotary spreader, it is inevitable that the rotation speed is low due to the large integration of the semiconductor integrated circuit and the large diameter of the substrate due to the high density. In this rinse process, when the substrate does not have a proper dissolution rate at the contact speed of the thinner composition and the fluctuation of the substrate due to the low rotational speed, bounding occurs and the use of the unnecessary thinner composition increases. In the low rotation rinse process due to the large diameter of such a substrate, a stronger dissolution rate of the thinner is required than the conventional high rotation rinse process.

In addition, volatility is required to easily volatilize and remain on the surface of the substrate after removing the photosensitive resin, the volatility is so low that when the thinner composition is not volatilized, the remaining thinner itself remains in various processes, in particular It may act as a contaminant in the subsequent etching process to reduce the yield of a semiconductor device or a flat panel display device.If the volatility is too high, the substrate rapidly cools and the variation of the thickness of the coated photoresist is increased and easily used in the air. It can be volatilized and cause contamination of cleanliness itself. As a result, all kinds of defects such as tailing and photoresist film attack are a direct cause of lowering the manufacturing yield of semiconductor devices or flat panel display devices.

Looking at the conventional thinner compositions are as follows.

Japanese Patent Application Laid-Open No. 63-69563 proposes a method of removing a thinner composition by contacting an unnecessary photoresist film of an edge upside part, an edge side part, and an edge back side part of a substrate. have. Examples of the solvent for removing the photoresist film include ethers such as cellosolve cellovolve acetate, propylene glycol ether, propylene glycol ether, and ether acetates such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like. Ester, such as ketones, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, is used. Disclosed is a method of removing the thinner composition by contacting the photosensitive film of the substrate, the flue part, and the back part with an unnecessary photosensitive film using the solvent as a thinner composition. Japanese Laid-Open Patent Publication No. Hei 4-42523 uses alkyl as a thinner composition. A method of using alkoxy propionate is disclosed.

In the case of ethylene glycol monoethyl ether acetate, the dissolution rate is excellent, but there is a problem in that it exhibits reproductive toxicity, such as high volatility and flammability, in particular leukopenia and induction of fetal abortion. In addition, since ethyl lactate has a high viscosity and a low dissolution rate, there is a problem that a sufficient washing effect cannot be obtained by itself.

In order to solve this problem, a method of mixing and using conventional single solvents has been researched and developed.

Japanese Unexamined Patent Application Publication No. Hei 4-130715 uses a thinner composition composed of a mixed solvent consisting of an alkyl pyrupinic acid solvent and methyl ethyl ketone. Japanese Laid-Open Patent Publication No. 7-146562 uses a thinner composition composed of a mixture of propylene glycol alkyl ether and 3-alkoxy propionic acid alkyls. Japanese Laid-Open Patent Publication No. H7-128867 uses a thinner composition composed of a mixture of propylene glycol alkyl ether and butyl acetate and ethyl lactate or a mixture of butyl acetate and ethyl lactate and propylene glycol alkyl ether acetate. Japanese Patent Application Laid-Open No. 7-160008 uses a thinner composition composed of a mixture of propylene glycol alkyl ether propionate and methyl ethyl ketone, or a mixture of propylene glycol alkyl ether propionate and butyl acetate. U.S. Patent No. 4,983,490 uses a mixed solvent of propylene glycol alkylether acetate and propylene glycol alkyl ether as thinner composition, while U.S. Patent No. 4,886,728 uses a mixture of ethyl lactate and methyl ethyl ketone as thinner composition. .

However, even with the above-described mixed solvents, there are many difficulties in the application of semiconductor devices and flat panel display devices, which are becoming increasingly integrated and large diameters.

For example, when a mixed solvent consisting of a solvent of alkyl pyrufinic acid and methyl ethyl ketone is used as the thinner composition, a 1,2-naphthaquinonediazide-based photosensitive agent having a high esterification rate among the photosensitive agents, which is one of the important components of the photosensitive film, is used. Solubility in water is poor, and when a highly volatile solvent such as a mixed solvent of propylene glycol alkyl ether propionate and butyl acetate is used as a thinner composition for rear cleaning, the thickness variation of the photoresist film is increased while the substrate is cooled. When a solvent having low volatility, such as a mixed solvent of ethyl lactate and methyl ethyl ketone, is used as the thinner composition, the cleaning ability of the substrate edge region is poor. In particular, when a solvent such as methyl pyruvate, ethyl pyruvate and the like is used as the thinner composition, it is known to corrode metal parts in the photosensitive waste liquid storage tank attached to the photosensitive film rotary spreader when used for a long time.

Therefore, in order to solve this problem, the development of a new thinner composition for removing a photosensitive resin is required.

An object of the present invention is to remove the unnecessarily attached photosensitive film used in the edge portion and the rear portion of the substrate used in the manufacturing method of the semiconductor device and the flat panel display device in a short time efficiently, in particular during the passivation process of the semiconductor device It is an object of the present invention to provide a thinner composition for removing a photosensitive resin that can be applied to a process and exhibits good effects. In addition, the thinner composition for removing the photosensitive resin of the present invention is to provide a photosensitive resin composition that is not toxic to the human body, there is no discomfort due to the smell, high work stability, and low corrosive effect.

The present invention

(a) an alkyl amide represented by Formula 1 below;

(b) alkyl pyrrolidone represented by the following formula (2); And

(c) Provides a thinner composition for removing a photosensitive film resin comprising a fluorinated acrylic copolymer.

<Formula 1>

In Formula 1, R ₁ , R ₂ and R ₃ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, provided that at least one of R ₁ , R ₂ and R ₃ is an alkyl group having 1 to 4 carbon atoms. .

<Formula 2>

In Formula 2, R ₄ and R ₅ are each independently an alkyl group having 1 to 4 carbon atoms unsubstituted or substituted with hydrogen or a hydroxyl group.

In addition, the present invention provides a method for manufacturing a semiconductor device and a flat panel display device by removing the unnecessary photosensitive film by spraying the thinner composition for removing the photosensitive resin to the edge portion and the rear portion of the substrate coated with the photosensitive resin composition. do.

Hereinafter, the present invention will be described in detail.

The (a) alkyl amide contained in the thinner composition for removing photosensitive resin of the present invention is represented by the following formula (1).

<Formula 1>

In Formula 1, R ₁ , R ₂ and R ₃ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, provided that at least one of R ₁ , R ₂ and R ₃ is an alkyl group having 1 to 4 carbon atoms. .

The alkyl amide (a) is used as a solvent in the thinner composition for removing the photosensitive resin, and increases the initial dissolution rate such as wafer, glass, plastic, stainless steel, etc. used in the manufacturing process of semiconductor devices and flat panel display devices. It serves to remove the spherical material consisting of the photosensitive material generated in the edge portion and the back portion of the substrate.

The (a) alkyl amides can be used in each of the pure grade of the semiconductor grade, filtered to the level of 0.1㎛ VLSI grade can be used.

The (a) alkyl amide is preferably included in 1 to 98% by weight based on the total weight of the thinner composition for removing a photosensitive resin. More preferably 30 to 49% by weight. When (a) the alkyl amide is contained in 1% by weight to 98% by weight, there is an advantage that the volatility and the solvent power are kept constant. In addition, when the (a) alkyl amide is contained in an amount of 30% by weight to 49% by weight, the dissolution rate is kept constant, such that tailing of the partially dissolved photoresist tail, called tailing, is applied to the rinse of the photoresist film applied to the substrate. There is no flow phenomenon, and there is an effect that no photoresist attack occurs in the rinse of the photoresist applied to the substrate.

As a specific example of the above (a) alkyl amide, one or two or more selected from the group consisting of N-methyl acetamide dimethyl acetamide, dimethyl formamide and dimethyl acetamide may be used, and in particular, dimethyl formamide may be used. It is preferable to use.

The (b) alkyl pyrrolidone included in the thinner composition for removing a photosensitive resin of the present invention is represented by the following formula (2).

<Formula 2>

In Formula 2, R ₄ and R ₅ are each independently an alkyl group having 1 to 4 carbon atoms unsubstituted or substituted with hydrogen or a hydroxyl group.

The (b) alkyl pyrrolidone is used as a solvent in the thinner composition for the photosensitive resin, and serves to increase the dissolution rate of the photosensitive resin together with the (a) alkyl amide. The (b) alkyl pyrrolidone can be used in each of the pure grade of the semiconductor grade, filtered to the level of 0.1 ㎛ of VLSI grade can be used.

The alkyl pyrrolidone (b) is preferably included in 1 to 98% by weight, more preferably 50 to 69% by weight based on the total weight of the thinner composition for the photoresist. When (b) the alkyl pyrrolidone is included in 1% by weight to 98% by weight, there is an advantage that the volatility and the dissolving power are kept constant. In addition, when the (b) alkyl pyrrolidone is contained in 50% by weight to 69% by weight, since the dissolution rate is kept constant, the partially dissolved photosensitive film tail called tailing in the rinse of the photosensitive film applied to the substrate ( There is an advantage that the flow of tail does not appear. In addition, there is an advantage that the photoresist attack does not appear in the rinse of the photoresist applied to the substrate.

Specific examples of the (b) alkyl pyrrolidone include 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, N-propyl pyrrolidone, N-hydroxymethyl pyrrolidone and N-hydroxyethyl pyrrolidone Etc., These can be used 1 type or in mixture of 2 or more types, It is preferable to use 1-methyl- 2-pyrrolidone especially.

The (c) fluorinated acrylic copolymer included in the thinner composition for removing a photosensitive resin of the present invention has excellent solubility in water and various solvents including (a) alkyl amide and (b) alkyl pyrrolidone. It acts as a nonionic surfactant. The (c) fluorinated acrylic copolymer has a weight average molecular weight of 1,000 to 10,000, the flash point (measured by the open cup method) 200 ℃, specific gravity 1.10 g / ml (25 ℃), viscosity (20 ℃) 2100 cst, surface tension is 24.0 mN / m (Wilhermy method) on ethyl lactate, it is preferable to use dilute and mixed with ethyl lactate. As the (c) fluorinated acrylic copolymer, commercially available products include F-475 manufactured by Dainippon Ink and Chemicals.

The (c) fluorinated acrylic copolymer is preferably included in 0.001 to 1% by weight based on the total weight of the composition. When the content of the (c) fluorinated acrylic copolymer is in the range of 0.001 to 1.0% by weight, it may exhibit excellent removal performance by lowering the dynamic surface tension at the interface to the photoresist. In addition, since the dissolving power to the photosensitive liquid is kept constant, there is an advantage that the volatility and cleaning power of the thinner at the end of the substrate are also kept constant. In addition, there is an advantage that can not prevent the malfunction of the sensor that detects the amount of liquid when using, since the bubbles are not generated badly.

In addition, the thinner composition for removing the photosensitive resin of the present invention is selected from the group consisting of propylene glycol monomethyl ether, n-butyl acetate, propylene glycol monomethyl ether acetate, gamma butyl lactone, methyl amyl ketone, ethyl lactate, and the like as an organic solvent. It may further comprise one or two or more compounds.

In addition, the present invention provides a method of manufacturing a semiconductor device or a flat panel display device using the thinner composition for removing the photosensitive resin.

In the method for manufacturing a semiconductor device and a flat panel display device using the photosensitive resin removing thinner composition of the present invention, the photosensitive resin is coated on a substrate, and the photosensitive resin removing thinner composition of the present invention is appropriately combined in a predetermined component ratio, and then the edge of the substrate. Spraying the portion and the rear portion to remove unnecessary photoresist.

The dropping and spraying amounts of the thinner composition for removing the photosensitive resin are used according to the type of the photosensitive resin and the thickness of the film to be used, and it is particularly preferable to select and use in the range of 5 to 50 cc / min. After spraying the thinner composition as described above, a fine circuit pattern may be formed through a subsequent photolithography process.

Subsequently, the semiconductor device and the flat panel display device may be manufactured by general techniques known in the art.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, the following examples are for illustrating the present invention and the present invention is not limited by the following examples.

Example  1 to 5 and Comparative example  1 to 3: For removing photosensitive resin Thinner  Preparation of the composition

The composition according to the composition ratio of Table 1 in a mixing tank equipped with a stirrer After the addition, stirring at a speed of 500rpm for 1 hour at room temperature to prepare a thinner composition for removing a photosensitive resin.

Thinner Composition Classification (wt%) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 NMP 60 60 50 50 50 60 DMF 39.9985 39.997 49.9985 39.9985 29.9985 40 PGMEA 85 PGME 10 10 15 80 n-BA 10 20 F-475 0.0015 0.003 0.0015 0.0015 0.0015

NMP: 1-methyl-2-pyrrolidone (1-methyl-2-pyrrolidone)

DMF: dimethyl formamide

PGMEA: propyleneglycol monomethylether acetate

PGME: propyleneglycol monomethylether

n-BA: n-butyl acetate

F-475: (Brand name, Dainippon & Chemicals, Fluorinated acrylic copolymer)

Experimental Example : For photosensitive resin composition Thinner  Unnecessary photoresist removal experiment of composition

After applying the photosensitive resin composition shown in Table 2 to a 4 inch silicon oxide substrate, the thinner composition according to Examples 1 to 5 and Comparative Examples 1 to 3 was subjected to the edge portion under the conditions described in Table 3. The experiment to remove the unnecessary photoresist of (Edge Bead Removing experiment: hereinafter referred to as EBR experiment) was carried out. The thinner compositions for removing the photosensitive resin according to Examples 1 to 5 and Comparative Examples 1 to 3 were supplied from a pressure vessel equipped with a pressure gauge, and the pressure was 1 kgf, and the flow rate of the thinner composition from the EBR nozzle was 10 to 30 cc / min. Then, by using an optical microscope and a scanning electron microscope to evaluate the removal of the unnecessary photosensitive film, the results are shown in Table 4 below.

Photosensitive resin composition type and film thickness division Composition type Composition Film thickness (㎛) Photosensitive Resin Composition A i-line positive PFI-DW64 1.3 μm Photosensitive resin composition B Deep UV Positive SSK-500MA 1.45 μm Photosensitive Resin Composition C Polyimide resin HD-8010-H3 12㎛

PFI-DW64: Product Name, Manufacturer: Dongwoo Fine Chem

SSK-500MA: Product Name, Manufacturer: Dongwoo Fine Chem

HD-8010-H3: Trade Name, Manufacturer: Acquid Micro System (HD Microsystems)

EBR experimental conditions division Rotation speed (rpm) Time (sec) Distribution conditions 300-2000 7 Spin coating Adjustable according to the photoresist thickness 15 EBR Condition 1 2000 20 EBR Condition 2 2000 25 Dry condition 1300 6

EBR Experimental Evaluation on Photosensitive Resin Compositions division EBR condition Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 I line positive 2000 rpm 20s ◎ ◎ ◎ ◎ ◎ ○ △ △ 2000 rpm 25 s ◎ ◎ ○ ◎ ◎ ○ × × Deep UV Positive 2000 rpm 20s ◎ ◎ ◎ ◎ ◎ ○ × △ 2000 rpm 25 s ◎ ◎ ◎ ○ ○ ○ × △ Polyimide 2000 rpm 20s ◎ ◎ ◎ ○ ○ × × × 2000 rpm 25 s ◎ ○ ○ ○ ○ ○ × ×

Note: EBR line uniformity is constant for the photoresist film after EBR.

○: Good linear state with EBR line uniformity of 75% or more on the photoresist film after EBR

(Triangle | delta): The shape of the edge part after EBR was distorted by the thinner melt action.

X: Tailing phenomenon occurs in the edge film after EBR

Through Table 4 above, the thinner compositions for removing the photosensitive resins of Examples 1 to 5 according to the present invention showed excellent EBR performance for all photoresist films, while Comparative Examples 1 to 3 were for suppressing penetration into the photoresist film. It was confirmed that the removability is remarkably inferior to the thinner composition for removing the photosensitive resin of the present invention according to Examples 1 to 5.

In addition, even when the rotational speed (rpm) conditions of the EBR were changed, the thinner compositions for removing the photosensitive resins of Examples 1 to 5 according to the present invention maintained an equally good shape. This shows that the thinner composition for removing the photosensitive resin according to the present invention does not show an effect only under specific conditions, but shows the same performance under various conditions.

The thinner composition for removing a photosensitive resin according to the present invention can be used to remove unnecessarily attached photoresist film in a short time efficiently in a short time. Applicable to the passivation process in the manufacturing process of the device and shows a good effect. In addition, the thinner composition for removing the photosensitive resin of the present invention has no toxicity to the human body, there is no discomfort due to the smell, high work stability and low corrosiveness.

Claims (9)

(a) an alkyl amide represented by Formula 1 below; (b) alkyl pyrrolidone represented by the following formula (2); And (c) A thinner composition for removing photoresist resin, comprising a fluorinated acrylic copolymer: <Formula 1>

In Formula 1, R ₁ , R ₂ and R ₃ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, provided that at least one of R ₁ , R ₂ and R ₃ is an alkyl group having 1 to 4 carbon atoms. . <Formula 2>

In Formula 2, R ₄ and R ₅ are each independently an alkyl group having 1 to 4 carbon atoms unsubstituted or substituted with hydrogen or a hydroxyl group. The method according to claim 1, The thinner composition for removing the photosensitive resin may contain 1 to 98% by weight of the (a) alkyl amide, 1 to 98% by weight of the (b) alkyl pyrrolidone and 0.001 to 1% by weight of the (c) fluorinated acrylic copolymer. Thinner composition for photosensitive resin removal characterized by including. The method according to claim 1, The thinner composition for removing the photosensitive resin may contain 30 to 49 wt% of the (a) alkyl amide, 50 to 69 wt% of the (b) alkyl pyrrolidone, and 0.001 to 1 wt% of the (c) fluorinated acrylic copolymer. Thinner composition for photosensitive resin removal characterized by including. The method according to claim 1, The (a) alkyl amide is a thinner composition for removing photosensitive resin, characterized in that one or two or more selected from the group consisting of N-methyl acetamide, dimethyl formamide and dimethyl acetamide. The method according to claim 1, (B) alkyl pyrrolidone is 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, A thinner composition for removing photosensitive resin, which is one or two or more selected from the group consisting of N-propyl pyrrolidone, N-hydroxymethyl pyrrolidone and N-hydroxyethyl pyrrolidone. The method according to claim 1, Said (c) fluorinated acrylic copolymer has a weight average molecular weight of 1,000 to 10,000 thinner composition for removing a photosensitive resin. The method according to claim 1, The thinner composition for removing the photosensitive resin is one or two selected from the group consisting of propylene glycol monomethyl ether, n-butyl acetate, propylene glycol monomethyl ether acetate, gamma butyl lactone, methyl amyl ketone and ethyl lactate as an organic solvent. The thinner composition for removing photosensitive resin further containing species or more. The method of manufacturing a semiconductor device or a flat panel display device, wherein the thinner composition for removing the photosensitive resin according to any one of claims 1 to 7 is sprayed onto the edge portion and the rear portion of the substrate to which the photosensitive resin composition is applied to remove unnecessary photoresist film. . The method according to claim 8, The injection amount of the thinner composition for removing the photosensitive resin is a manufacturing method of a semiconductor device or a flat panel display device, characterized in that 5 to 50cc / min.