KR101672720B1 - Polymer for coating photoresist pattern and method for forming pattern for semiconductor device using the same - Google Patents

Polymer for coating photoresist pattern and method for forming pattern for semiconductor device using the same Download PDF

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KR101672720B1
KR101672720B1 KR1020090016981A KR20090016981A KR101672720B1 KR 101672720 B1 KR101672720 B1 KR 101672720B1 KR 1020090016981 A KR1020090016981 A KR 1020090016981A KR 20090016981 A KR20090016981 A KR 20090016981A KR 101672720 B1 KR101672720 B1 KR 101672720B1
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photoresist pattern
polymer
group
formula
coating
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KR20100098024A (en
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이정열
이재우
김덕배
김재현
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주식회사 동진쎄미켐
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Priority to PCT/KR2010/001227 priority patent/WO2010098618A2/en
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/40Treatment after imagewise removal, e.g. baking
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers

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Abstract

A polymer for photoresist pattern coating capable of increasing the resolution of a lithography process and a method for forming a pattern of a semiconductor device using the same are disclosed. The photoresist pattern coating polymer is represented by the following formula.

Figure 112009012399513-pat00001

In the above formulas, R * is independently a hydrogen atom or a methyl group (-CH 3 ), R 1 is a linear or cyclic hydrocarbon group having 3 to 6 carbon atoms and 1 to 2 nitrogen atoms, and R 2 is a group having 5 to 20 carbon atoms X, y, and z are mole% of each repeating unit of the repeating units constituting the polymer of the above formula, x is 5 to 90 mol%, y is 5 to 60 mol %, and z is 5 to 30 mol%.

Lithography, resolution, photoresist, pattern coating, polymer

Description

[0001] The present invention relates to a polymer for photoresist pattern coating and a method of forming a pattern of a semiconductor device using the polymer.

The present invention relates to a polymer for photoresist pattern coating, and more particularly, to a polymer for photoresist pattern coating capable of increasing the resolution of a lithography process and a method of forming a pattern of a semiconductor device using the same.

As the degree of integration of semiconductor devices increases, a photolithography process capable of forming an ultrafine photoresist pattern having a line width of 80 nm or less is required. In a typical photolithography process, a photoresist composition containing a photosensitive polymer and a solvent is coated on a substrate such as a silicon wafer used for manufacturing an integrated circuit, and the resultant is baked to evaporate the solvent, Thereby forming a film-shaped photoresist film. Next, by irradiating light of a predetermined pattern from the exposure source and exposing the photoresist film according to the pattern of the exposure source, the chemical properties of the photosensitive polymer are changed in the exposed area. Examples of the light used for such exposure include visible light, ultraviolet (UV) light, electron beam, X-ray, and the like. After the exposure, the exposed photoresist film is treated with a developer solution to selectively dissolve and remove the exposed or unexposed portions of the photoresist film to form a photoresist pattern.

In such a photolithography process, various techniques for increasing the resolution of the photoresist pattern have been developed. For example, PCT International Publication Nos. WO 2008/122884 and EP 1757989 disclose a method of coating a photoresist pattern with a polymer to reduce the space between patterns. 1 is a view showing an example of a conventional method of forming a fine photoresist pattern. 1, in the conventional photoresist pattern forming method, a photoresist film 20 is formed on the substrate 10 (FIG. 1A), and the photoresist film 20 is patterned into a predetermined shape A photoresist pattern 22 is formed by exposing and developing the photoresist pattern 22 with an image of the photoresist pattern 22 and then a shrink material 30 is coated on the photoresist pattern 22 formed thereon (C in Fig. 1). The substrate on which the line width reduction polymer 30 is coated is heated so that the photoresist pattern 22 and the line width reduction polymer 30 are bonded to each other to form the boundary layer 32 The open space between the photoresist patterns 22 is shrunk by developing the unreacted line width reduction polymer 30 with a developing solution such as water (E in FIG. 1) A photoresist pattern having a critical dimension can be formed. The photoresist pattern forming method shown in FIG. 1 is to reduce the size (size) of C / H (contact hole) in which the primary pattern is formed.

An object of the present invention is to provide a polymer for photoresist pattern coating which can increase the resolution of a lithography process.

Another object of the present invention is to provide a method of forming a pattern of a semiconductor device having a high resolution by using a polymer for photoresist pattern coating.

It is still another object of the present invention to provide a method of forming a pattern of a semiconductor device capable of forming a double pattern in a space between lines using self alignment of the pattern .

In order to achieve the above object, the present invention provides a polymer for photoresist pattern coating represented by the following Chemical Formula 1.

[Chemical Formula 1]

Figure 112009012399513-pat00002

In Formula 1, R * are each independently a hydrogen atom or a methyl group (-CH 3), R 1 is a group having 3 to 6 carbon atoms and a nitrogen number of 1 to 2 linear or cyclic hydrocarbon group, R 2 is 5 to 20 carbon atoms X, y, and z are mole percentages of the respective repeating units of the repeating units constituting the polymer of Formula 1, x is from 5 to 90 mol%, y is from 5 to 20 mol% 60 mol%, and z is 5 to 30 mol%.

The present invention also provides a polymer for photoresist pattern coating represented by Formula 1 above; And a solvent for dissolving the polymer for photoresist pattern coating. According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming a photoresist film by applying a first photoresist on a substrate; exposing and developing the photoresist film to form a first photoresist pattern; A composition for a photoresist pattern coating comprising a polymer for photoresist pattern coating represented by Chemical Formula 1 and a solvent for dissolving the polymer for photoresist pattern coating is applied to the first photoresist pattern and the solvent is evaporated, ; Reacting the coating film with the first photoresist pattern to form a boundary layer covering the first photoresist pattern and developing and removing the unreacted coating film; Applying a second resist to a space between the boundary layers to form a second resist pattern; And developing and removing the boundary layer to leave the first photoresist pattern and the second resist pattern.

By using the polymer according to the present invention, the first photoresist pattern is coated, developed with deionized water or the like, and then a second (photo) resist pattern is formed again on the developed space region, The line width of the portion can be reduced. In this way, by forming a double pattern in the space between the lines of the first photoresist pattern so that the second (photoresist) pattern is self-aligned, in the process of forming the second photoresist pattern using the equipment It is possible to reduce an alignment error problem that may occur.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The polymer for photoresist pattern coating according to the present invention forms a boundary layer (coating film) that reacts with the photoresist pattern to cover the photoresist pattern, and is represented by the following chemical formula (1).

In the formula (1), R * is independently a hydrogen atom or a methyl group (-CH 3 ), R 1 is a linear or cyclic hydrocarbon group having 3 to 6 carbon atoms and 1 to 2 nitrogen atoms, preferably imidazole imidazole group, and lactam group, or a carbonyl group containing an amine group such as an amide group. Also, R 2 is an alkoxybenzene group or an alkoxycarbonyl group having 5 to 20 carbon atoms, preferably 5 to 13 carbon atoms, and the alkoxy group of R 2 may be a linear or cyclic alkoxy group, Or an alkoxy group having 1 to 2 carbon atoms to which a linear or cyclic alkoxy group is bonded. Specific examples of the alkoxy group contained in R 2 include a methyladamantanoxy group, a 1-ethoxy-ethoxy group, a 1-cyclohexylmethoxy-ethoxy group, a cyclohexyloxy-methoxy group and the like . In the above formula (1), x, y, and z are mole percentages of the respective repeating units of the repeating units constituting the polymer of Formula 1, x is 5 to 90 mol%, preferably 10 to 80 mol% More preferably 15 to 70% by weight, y is 5 to 60% by mol, preferably 10 to 50% by mol, more preferably 15 to 40% by mol, z is 5 to 30% by mol, 10 to 20 mol%, and more preferably 12 to 18 mol%. If the content of x is too small, the solubility in deionized water is lowered, and if it is too large, the adhesion to the photoresist pattern may be deteriorated. If the content of y is too small, the adhesion to the pattern may be lowered and the pattern may not be adhered to the pattern. If the content is too large, the solubility in deionized water may decrease. Further, even when the content of z is too small, the solubility in deionized water may be lowered.

Specific examples of the polymer for photoresist pattern coating according to the present invention may be represented by the following general formulas (2a) to (2i). In the following formulas (2a) to (2i), x, y and z are as defined in the above formula (1).

The polymer for photoresist pattern coating according to the present invention,

Figure 112009012399513-pat00013
, R * , R 1 , R 2, etc., can be prepared by polymerizing a vinyl monomer in a conventional manner. In this case, a conventional polymerization initiator such as azobis (isobutyronitrile) (AIBN) have. In the polymer according to the present invention, the content of each repeating unit is proportional to the content of the monomer used. The polymer for photoresist pattern coating according to the present invention may be a block or a random copolymer and has a weight average molecular weight (Mw) of preferably 5,000 to 100,000, more preferably 5,000 to 20,000. The polydispersity (PD) of the polymer is preferably 1.0 to 5.0, more preferably 1.0 to 2.0. If the weight average molecular weight and the polydispersity are out of the above ranges, the physical properties of the coating film for coating the photoresist pattern may be deteriorated. Since the polymer for photoresist pattern coating according to the present invention contains an amine group in the molecule, it is easy to adhere to the photoresist pattern, and coating is possible without damaging the photoresist pattern. Further, since the polymer for photoresist pattern coating according to the present invention contains an alkoxybenzene group or an alkoxycarbonyl group as R 2 , even after adhesion by exposure and heating, Can be easily dissolved and removed, and the contrast of the developing process is excellent.

The polymer for photoresist pattern coating according to the present invention is dissolved in a solvent and used in the form of a composition. The solvent for the photoresist pattern coating composition may be water, preferably deionized water. If necessary, a mixed solvent of water and alcohol may be used. In the composition for coating a photoresist pattern, the content of the polymer represented by the general formula (1) is 0.5 to 30% by weight, preferably 3 to 10% by weight, and the remaining component is a solvent. If the content of the polymer is too small, the polymer layer remaining after the coating is too thin to form a coating film having a desired thickness. If the content of the polymer is too large, there is a fear that coating uniformity is lowered. In the composition for coating a photoresist pattern according to the present invention, examples of alcohols that can be used together with water include lower alcohols having 1 to 4 carbon atoms such as methanol and ethanol, 0 to 50% by weight, preferably 1 to 50% by weight, more preferably 5 to 25% by weight. If the content of the alcohol component is too small, there is a fear that the coating uniformity is lowered. If the content of the alcohol component is too large, there is a fear that the initial pattern is dissolved to form the secondary pattern. If necessary, the composition for photoresist pattern coating according to the present invention may further contain a photoacid generator (PAG), a resist stabilizer (Quencher), an organic base, a surfactant, and the like. The photoacid generator serves to deprotect the protecting group of the polymer for photoresist pattern coating by generating an acid by exposure to light. Any compound capable of generating an acid by light can be used , Preferably a sulfur-based compound such as an organic sulfonic acid, and an onium salt-based compound such as an onium salt, or the like. Non-limiting examples of the photoacid generator include phthalimidotrifluoro methane sulfonate, dinitrobenzyl tosylate, n-decyl disulfone, naphthylimidotriene, Naphthylimido trifluoromethane sulfonate, diphenyl iodide salt hexafluorophosphate, diphenyl iodide salt hexafluoroarsenate, diphenyl iodide salt hexafluoroantimonate, diphenyl para methoxy phenyl sulfonium triflate, Triphenylsulfonium hexafluoroantimonate, triphenylsulfonium triflate, dibutylnaphthylsulfonium triflate, mixtures thereof, and the like can be given. When the photoacid generator is used, the content thereof is preferably 0 to 20 parts by weight, more preferably 0.05 to 20 parts by weight, and most preferably 0.1 to 10 parts by weight based on 100 parts by weight of the polymer. If the content of the photoacid generator is too small, the sensitivity of the polymer to light may be lowered and the deprotection of the protecting group may be insufficient. When the content of the photoacid generator is too large, excessive acid is generated in the photoacid generator, There is a concern. As the surfactant that can be used in the present invention, it is preferable to use a water-soluble surfactant, and an anionic surfactant, a cationic surfactant and an amphoteric surfactant can be used. Examples thereof include alkylbenzenesulfonic acid salts, Cargo, quaternary ammonium salts, alkylpyridinium salts, amino acids, sulfoneimides and sulfonamide surfactants may be used alone or in combination. The surfactant is used in an amount of 0.01 to 2 parts by weight, preferably 0.1 to 1 part by weight based on 100 parts by weight of the composition for coating the entire photoresist pattern. If the amount of the surfactant used is too small, the uniformity of the coated portion may deteriorate during the film formation. If the surfactant is used in an excessively large amount, the loss of the film may increase during the removal of the coating film with water, There is a fear that it will not be able to do.

Next, a method of forming a pattern of a semiconductor device according to the present invention will be described with reference to FIG. In the pattern formation method of the semiconductor device shown in Fig. 2, the photoresist pattern coating step is substantially the same as that shown in Fig. That is, a first photoresist is coated on the substrate 10 such as a silicon wafer or aluminum to form a photoresist film 20 (FIG. 2A), and the photoresist film 20 is patterned into a predetermined shape (FIG. 1B), the composition for photoresist pattern coating according to the present invention is applied to the first photoresist pattern 22, and the solvent is evaporated Thereby forming a coating film 30 (FIG. 2C). Next, the first photoresist pattern 22 and the polymer for photoresist pattern coating are adhered to each other or the first photoresist pattern 22 is coated with an acid (e.g., acid is diffused into the polymer for photoresist pattern coating to form a cap layer 32 covering the first photoresist pattern 22 (FIG. 2D), and then the unreacted coating film 30 is washed with water (E in FIG. 2) with a developing solution such as an alcohol, an aqueous alkaline solution, a mixture thereof, or the like to shrink the open space between the photoresist patterns 22.

As described above, the first photoresist pattern 22 is coated with the boundary layer 32 to reduce the width of the space, and the second resist is applied to the space having the reduced width to form the second resist pattern 42 (FIG. 2F). The strength of the second resist pattern 42 can be improved by exposing or heating the second resist pattern 42 formed as described above and diffusing the acid to the second resist pattern 42 have. In this case, the second resist is preferably a photosensitive photoresist whose physical properties are changed by exposure. Next, the alkaline aqueous solution obtained by dissolving an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide (TMAH) in a concentration of 0.1 to 10% by weight is used again to develop the boundary layer (32, CAP material) And the first photoresist pattern 22 and the second photoresist pattern 42 are left (G in FIG. 2), whereby a photoresist pattern having a reduced space width can be formed. Since the solubility of the first and second photoresist patterns 22 and 42, the coating layer 30 and the boundary layer 32 varies depending on the properties of the material itself, the heating and exposure, and the like, By appropriately adjusting the developing time, only the boundary layer 32 can be selectively developed. After the first and second photoresist patterns 22 and 42 are formed as described above, the substrate 10 is etched using the formed photoresist patterns 22 and 42 as a mask, The pattern of the semiconductor element can be formed by processing the substrate 10 in such a manner as to change the physical properties of the semiconductor element.

As the photoresist for forming the first and second photoresist patterns 22 and 42, a conventional ArF or KrF resist can be used. By forming the second photoresist pattern 42 in the form of a line, for example, in the space area of the first photoresist pattern 22 as described above, it is possible to form a pattern having an excellent resolution of about 30 nm. In such a method of forming a pattern of a semiconductor device, the polymer for photoresist pattern coating according to the present invention is used as a capping material for securing a space for forming a second pattern so as to form a double pattern do.

Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples are intended to further illustrate the present invention and are not intended to limit the scope of the present invention.

[Example 1-1] Preparation of polymer represented by formula (2a)

11.1 g (0.1 mol) of 1-vinyl-pyrrolidone (hereinafter referred to as VP), 11.4 g (0.08 mol) of acrylic acid-2-dimethylamino-ethyl ester (hereinafter referred to as DAEMA) (0.022 mol) and azobis (isobutyronitrile) (AIBN) (0.7 g) were dissolved in 100 g of acetonitrile, and the solution was subjected to freezing method Degassed using an ampoule and the degassed reaction was polymerized at 70 < 0 > C for 24 hours. After completion of the polymerization reaction, the reaction product is slowly added dropwise to an excess amount of diethyl ether to precipitate the product, which is then dissolved again in acetonitrile, and the dissolved product is re-precipitated in diethyl ether to obtain the polymer . Weight average and number average molecular weight (Mw, Mn) and polydispersity (PD) of the synthesized polymer were measured by gel permeation chromatography (GPC) (GPC analysis: Mn = 28,600, Mw = 74,500, PD = 2.60).

[Example 1-2] Production of polymer represented by the formula (2b)

Except that 7.9 g (0.08 mol) of dimethyl acrylamide (hereinafter DMAA) was used in place of 11.4 g (0.08 mol) of 2-acrylic acid-2-dimethylamino-ethyl ester (DAEMA) To prepare a polymer represented by the formula (2b). Weight average and number average molecular weight (Mw, Mn) and polydispersity (PD) of the synthesized polymer were measured by GPC (GPC analysis: Mn = 25,300, Mw = 71,100, PD = 2.81).

[Example 1-3] Preparation of polymer represented by formula (2c)

Except that 11.1 g (0.08 mol) of vinylcaprolactam (hereinafter referred to as VC) was used in place of 11.4 g (0.08 mol) of 2-acrylic acid-2-dimethylamino-ethyl ester (DAEMA) To prepare a polymer represented by the formula (2c). Weight average and number average molecular weight (Mw, Mn) and polydispersity (PD) of the synthesized polymer were measured by GPC (GPC analysis: Mn = 31,700, Mw = 76,100, PD = 2.40).

[Example 1-4] Preparation of a polymer represented by the formula (2d)

Except that 10.1 g (0.08 mol) of 1-vinyl-piperidin-2-one was used in place of 11.4 g (0.08 mol) of 2-acrylic acid-2-dimethylamino-ethyl ester (DAEMA) The polymer represented by the formula (2d) was prepared in the same manner as in (1). Weight average and number average molecular weight (Mw, Mn) and polydispersity (PD) of the synthesized polymer were measured by GPC (GPC analysis: Mn = 26,000, Mw = 75,600, PD = 2.91).

[Example 1-5] Preparation of polymer represented by formula (2e)

Except that 7.5 g (0.08 mol) of vinylimidazole (hereinafter referred to as VI) was used in place of 11.4 g (0.08 mol) of 2-acrylic acid-2-dimethylamino-ethyl ester (DAEMA) The polymer represented by the general formula (2e) was prepared in the same manner. Weight average and number average molecular weight (Mw, Mn) and polydispersity (PD) of the synthesized polymer were measured by GPC (GPC analysis: Mn = 27,000, Mw = 81,000, PD = 3.00).

[Example 1-6] Preparation of polymer represented by formula (2f)

(0.02 mol) of 1- (1- (cyclohexylmethoxy) ethoxy) -4-vinyl-benzene in place of 3.84 g (0.02 mol) of 1- (1-ethoxy-ethoxy) , The polymer represented by the general formula (2f) was prepared in the same manner as in Example 1-5. Weight average and number average molecular weight (Mw, Mn) and polydispersity (PD) of the synthesized polymer were measured by GPC (GPC analysis: Mn = 26,100, Mw = 67,500, PD = 2.59).

[Example 1-7] Preparation of polymer represented by formula (2g)

(0.02 mol) of acrylic acid 1-methyl-cyclopentyl ether instead of 3.84 g (0.02 mol) of 1- (1-ethoxy- 5, a polymer represented by formula (2g) was prepared. Weight average and number average molecular weight (Mw, Mn) and polydispersity (PD) of the synthesized polymer were measured by GPC (GPC analysis: Mn = 26,200, Mw = 46,100, PD = 1.76).

[Example 1-8] Preparation of polymer represented by formula (2h)

Except that 3.68 g (0.02 mol) of acrylic acid cydohexyloxymethyl ether was used in place of 3.84 g (0.02 mol) of 1- (1-ethoxy-ethoxy) -4-vinyl- A polymer represented by the formula (2h) was prepared in the same manner. Weight average and number average molecular weight (Mw, Mn) and polydispersity (PD) of the synthesized polymer were measured by GPC (GPC analysis: Mn = 19,900, Mw = 58,900, PD = 2.96).

[Example 1-9] Preparation of polymer represented by formula (2i)

Except that 4.68 g (0.02 mol) of 2-methyl-acrylic acid- 1- methyl-adamantanyl-ether was used instead of 3.84 g (0.02 mol) of 1- (1-ethoxy-ethoxy) , A polymer represented by the formula (2i) was prepared in the same manner as in Example 1-5. Weight average and number average molecular weight (Mw, Mn) and polydispersity (PD) of the synthesized polymer were measured by GPC (GPC analysis: Mn = 19,600, Mw = 61,300, PD = 3.13).

[Examples 2-1 to 2-10] Preparation of photoresist pattern coating composition

As shown in the following Table 1, 2.7 g of each of the polymers for photoresist pattern coating (Formulas 2a to 2i) synthesized in Examples 1-1 to 1-9, 2.7 g of a water-soluble surfactant (sulfonamide-based interface (Triphenylsulfonium triflate) (0.15 g) was completely dissolved in 17.0 g of deionized water or a mixed solvent of deionized water and isopropanol 6: 4, followed by filtration through a 0.2 mu m disk filter to obtain a photoresist To prepare a composition for pattern coating.

division Polymer usage Surfactants Photoacid generator Deionized water Alcohol Example 2-1 Formula 2a 2.7g 0.3 g - 17g - Example 2-2 2b 2.7g 0.3 g - 17g - Example 2-3 Formula 2c 2.7g 0.3 g - 17g - Examples 2-4 2d 2.7g 0.3 g - 17g - Example 2-5 2e 2.7g 0.3 g - 17g - Examples 2-6 2f 2.7g 0.3 g - 17g - Examples 2-7 2g 2.7g 0.3 g - 17g - Examples 2-8 2h 2.7g 0.3 g - 17g - Examples 2-9 2i 2.7g 0.3 g - 17g - Examples 2-10 Formula 2c 2.7g 0.3 g 0.15 g 10.2 g 6.8 g

[Examples 3-1 to 3-10] Pattern formation of a semiconductor device using a composition for photoresist pattern coating

2 g of a photoresist polymer for ArF (molecular weight (Mw): 10,100, polydispersity (PD): 1.89, a: b: c (mol%) = 45:40:15) 0.02 g of triflate and 0.01 g of triethanolamine were dissolved in 10 g of propylene glycol monomethyl ether acetate (PGMEA), followed by filtration through a 0.2 mu m filter to prepare a photoresist composition.

A 50 nm 1: 3 line and space pattern (first photoresist pattern) was formed using the photoresist composition. The photoresist pattern coating compositions prepared in Examples 2-1 to 2-10 were spin-coated on top of the wafer on which the first photoresist pattern was formed to form a thin film. Then, the thin film was baked in an oven or a hot plate at 60 ° C for 60 seconds Soft baked and immersed in an aqueous solution of deionized water or 2.38 wt% tetramethylammonium hydroxide (TMAH) for 60 seconds and developed to coat the photoresist pattern. Table 2 shows the line width variation of the lines of the coated pattern.

division The line width of the primary pattern,
CD (Critical Dimension)
After the first photoresist pattern coating,
Line width
Example 3-1 50 nm 71 nm Example 3-2 50 nm 68 nm Example 3-3 50 nm 72 nm Example 3-4 50 nm 66 nm Example 3-5 50 nm 65 nm Examples 3-6 50 nm 68 nm Examples 3-7 50 nm 71 nm Examples 3-8 50 nm 61 nm Examples 3-9 50 nm 63 nm Examples 3-10 50 nm 61 nm

Next, 2 g of KrF photoresist polymer (molecular weight (Mw): 14,800, polydispersity (PD): 2.02, a: b (mol%) = 65:35) represented by the following formula 4 and 0.01 g of triethanolamine And dissolved in 10 g of propylene glycol monomethyl ether acetate (PGMEA), followed by filtration through a 0.2 mu m filter to prepare a photoresist composition.

In order to form a secondary pattern on the space portion of the primary photoresist pattern, the photoresist composition (resist for the second pattern) was spin-coated on the wafer and soft-heat-treated for 60 seconds in an oven or a hot plate at 120 캜 Then, the heat-treated wafer was immersed in an aqueous 2.38 wt% tetramethylammonium hydroxide (TMAH) solution for 60 seconds to develop the coating, thereby removing the coated portion. As described above, a secondary resist pattern having a height lower than that of the primary photoresist pattern was formed in the space portion of the first photoresist pattern, and a scanning electron micrograph of the resist pattern formed using the compound of Example 3-3 is shown in FIG. 3 Respectively. It can be seen from FIG. 3 that by the self double patterning process according to the present invention, the second resist pattern can be easily formed in the 1: 3 line and the spacer portion. Therefore, when the second resist pattern is formed using the polymer for photoresist pattern coating according to the present invention, it is unnecessary to align the semiconductor exposure apparatus mask using the conventional 193 nm, 248 nm and other light sources, And a self-double patterning process can be performed only by the developing process.

1 is a view showing an example of a conventional method of forming a fine photoresist pattern.

2 is a view showing an example of a pattern forming method of a semiconductor device according to the present invention.

3 is an electron micrograph of a resist pattern formed according to a method of forming a pattern of a semiconductor device according to the present invention.

Claims (13)

1. A photoresist pattern coating polymer represented by the following formula (1). [Chemical Formula 1]
Figure 112016042561661-pat00016
Wherein R * is independently a hydrogen atom or a methyl group (-CH 3 ), R 1 is a linear or cyclic hydrocarbon group having 3 to 6 carbon atoms containing 1 to 2 nitrogen atoms, and R 2 is a carbon number X, y and z are mole% of each repeating unit with respect to all repeating units constituting the polymer of formula (1), x is 10 to 80 mol%, y Is 5 to 60 mol% and z is 5 to 30 mol%, and in the alkoxycarbonyl group of R 2 , the alkoxy group is an alkoxy group having 1 to 2 carbon atoms to which a linear or cyclic alkoxy group is bonded.
2. The polymer of claim 1, wherein R < 1 > is a carbonyl group containing a heterocyclic group or an amine group. 2. The polymer of claim 1, wherein R < 1 > is an imidazole group or a lactam group. The photoresist pattern coating polymer according to claim 1, wherein the polymer for photoresist pattern coating has a weight average molecular weight (Mw) of 5,000 to 100,000. The method of claim 1, wherein the polymer for coating a photoresist pattern comprises
Figure 112015108841664-pat00017
(Formula 2a),
Figure 112015108841664-pat00018
(Formula 2b),
Figure 112015108841664-pat00019
(Formula 2c),
Figure 112015108841664-pat00020
(Formula 2d),
Figure 112015108841664-pat00021
(Formula 2e),
Figure 112015108841664-pat00022
(2f) and
Figure 112015108841664-pat00024
Wherein x, y and z are as defined in the above formula (1). 2. The photoresist pattern coating according to claim 1,
A polymer for photoresist pattern coating represented by Formula 1 below; And And a solvent for dissolving the polymer for photoresist pattern coating. [Chemical Formula 1]
Figure 112016042561661-pat00026
Wherein R * is independently a hydrogen atom or a methyl group (-CH 3 ), R 1 is a linear or cyclic hydrocarbon group having 3 to 6 carbon atoms containing 1 to 2 nitrogen atoms, and R 2 is a carbon number X, y and z are mole% of each repeating unit with respect to all repeating units constituting the polymer of formula (1), x is 10 to 80 mol%, y Is 5 to 60 mol% and z is 5 to 30 mol%, and in the alkoxycarbonyl group of R 2 , the alkoxy group is an alkoxy group having 1 to 2 carbon atoms to which a linear or cyclic alkoxy group is bonded.
The composition for photoresist pattern coating according to claim 6, wherein the solvent for dissolving the polymer for photoresist pattern coating is deionized water. The photoresist pattern coating solution according to claim 6, wherein the solvent for dissolving the polymer for photoresist pattern coating is a mixed solvent of water and alcohol, and the amount of the alcohol is 1 to 50 wt% Composition. 7. The composition for photoresist pattern coating according to claim 6, further comprising 0.05 to 20 parts by weight of a photoacid generator based on 100 parts by weight of the polymer for photoresist pattern coating. 7. The composition of claim 6 further comprising a surfactant selected from the group consisting of alkylbenzenesulfonic acid salts, higher amine halides, quaternary ammonium salts, alkyl pyridinium salts, amino acids, sulfonimides, and sulfonamide surfactants And the surfactant is used in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the total composition for a photoresist pattern coating. Forming a photoresist film by applying a first photoresist on a substrate, exposing and developing the photoresist film to form a first photoresist pattern; A composition for a photoresist pattern coating comprising a polymer for photoresist pattern coating represented by Chemical Formula 1 and a solvent for dissolving the polymer for photoresist pattern coating is applied to the first photoresist pattern and the solvent is evaporated, , ≪ / RTI > [Chemical Formula 1]
Figure 112016042561661-pat00027
Wherein R * is independently a hydrogen atom or a methyl group (-CH 3 ), R 1 is a linear or cyclic hydrocarbon group having 3 to 6 carbon atoms containing 1 to 2 nitrogen atoms, and R 2 is a carbon number X, y and z are mole% of each repeating unit with respect to all repeating units constituting the polymer of formula (1), x is 10 to 80 mol%, y Is 5 to 60 mol% and z is 5 to 30 mol%, and in the alkoxycarbonyl group of R 2 , the alkoxy group is an alkoxy group having 1 to 2 carbon atoms to which a linear or cyclic alkoxy group is bonded; Reacting the coating film with the first photoresist pattern to form a boundary layer covering the first photoresist pattern and developing and removing the unreacted coating film; Applying a second resist to a space between the boundary layers to form a second resist pattern; And Removing the boundary layer by developing, and leaving the first photoresist pattern and the second resist pattern.
12. The method according to claim 11, wherein the development of the unreacted coating film is performed by water, and the development of the boundary layer is performed by an aqueous alkali solution having a concentration of 0.1 to 10% by weight. 12. The method according to claim 11, further comprising the step of exposing or heating the second resist pattern to improve the strength of the second resist pattern.
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