Chemically amplified positive photoresist composition for improving pattern profile and enhancing adhesion

Abstract

The present invention relates to a chemically amplified positive photoresist composition for improving a pattern profile and enhancing adhesion as a photoresist composition capable of exposure using a light source having a wavelength of 248 nm, in order to achieve a vertical profile without pattern collapse, the chemically amplified positive photoresist composition having a thickness of 1 [mu] m or less with respect to the total weight of the composition, and the chemically amplified positive photoresist composition having a thickness of 1 [mu] m or less, as a photoresist composition capable of exposure using a light source having a wavelength of 248 nm, and having a thickness of 1 [mu] m or less with respect to the total weight of the composition. Comprising 1 to 5 wt% of a polyhydric alcohol additive represented by Chemical Formulae 1 to 8, and a method for manufacturing the same.

Description

Technical Field

[0001] The invention relates to a chemically amplified positive photoresist composition for improving pattern profile and enhancing adhesion between pattern and substrate. Background Art

[0002] Recently, with the development of semiconductor manufacturing process technology, the miniaturization and high integration of semiconductor elements are required, and the technology of realizing ultra-fine patterns with line widths below tens of nanometers is required. The progress of the technology for forming such ultra-fine patterns depends on light sources with smaller wavelengths, the development of process technology based on light sources, and the development of photoresists suitable for light sources.

[0003] Photoresist is used in the photolithography process for forming various patterns. Photoresist refers to a photosensitive resin that can change its solubility in a developer under the action of light, thereby obtaining an image corresponding to the exposure pattern.

[0004] The photoresist pattern forming method includes negative tone development (NTD) using a negative tone developer and positive tone development (PTD) using a positive tone developer.

[0005] The pattern forming method using the negative tone developer is a method of forming a pattern by selectively dissolving and removing the non-exposed area using the negative tone developer, while the pattern forming method using the positive tone developer is a method of forming a pattern by selectively dissolving and removing the exposed area using the positive tone developer.

[0006] Compared with the pattern forming method using the positive tone developer, the pattern forming method using the negative tone developer can also realize an inverted pattern in a contact hole pattern or a groove pattern that is difficult to form due to insufficient exposure, so it is easy to form a pattern when realizing the same pattern, and an organic solvent is used as a developer for removing the unexposed part, so that the photoresist pattern can be formed more efficiently.

[0007] On the other hand, generally, the photolithography process using the photoresist composition includes: a process of coating the photoresist on a wafer; a soft baking process of heating the coated photoresist to evaporate the solvent; a process of imaging with the help of a light source passing through a photomask; a process of forming a pattern using a developer according to the solubility difference between the exposed part and the non-exposed part; and a process of etching it to complete the circuit.

[0008] The photoresist composition is composed of a photosensitive agent (Photo Acid Generator) that generates acid by irradiation with an excimer laser, a base resin and other additives. In the base resin, a polystyrene polymer is basically used as a structure containing a hydroxyl group in a phenol structure. As a photosensitive agent, any material that can generate acid (H+) at a specific wavelength is acceptable, and sulfonium salts, sulfonyl diazonium salts, benzene sulfonyls, iodine, chlorine, carboxylic acids, etc. are mainly used.

[0009] In addition, the light source mainly used in the above-mentioned process is a wavelength region of 365nm to 193nm using i-line, KrF excimer laser, ArF excimer laser light source, and the shorter the wavelength, the finer the pattern can be formed.

[0010] Among them, although the ArF laser (193nm) system was developed later, the KrF laser (248nm) photoresist has also been pursuing research and development of optical micro-processing. As a reason for this, the following reasons can be cited, that is, although the development of the second-generation ArF photoresist still has unsatisfactory aspects, if the KrF to i-Line photoresist is continued to be used, the effect of reducing costs in the mass production of semiconductors is great. Corresponding to the development of this technology, the performance of KrF to i-Line photoresists should also be improved. A representative example is that with the high integration, the thickness of the photoresist is required to be gradually reduced, so it is urgent to develop a photoresist with enhanced dry etching resistance. In addition, the characteristics required include high resolution, wide depth of focus (DOF (Depth Of Focus)) margin, formation of defect-free film, adhesion to the substrate, high contrast (Contrast), fast sensitivity, chemical stability, etc.

[0011] As mentioned above, previous patents for KrF to i-Line photoresist technology include Korean Patent Gazette No. 10-0047038 "Chemically amplified positive photoresist composition", Korean Patent Gazette No. 10-1363842 "Chemically amplified positive photoresist composition and anti-etching pattern forming method using the same", Korean Patent Gazette No. 10-1204915 "Photoresist polymer, photoresist composition containing the same and photoresist pattern forming method using the same", Korean Patent Gazette No. 10-0273108 "Copolymer for photoresist preparation and chemically amplified positive photoresist composition containing the same", Korean Patent Gazette No. 10-1655947 "Negative photoresist composition for KrF laser with high resolution and high aspect ratio", Korean Patent Gazette No. 10-1977886 "Chemically amplified positive photoresist composition for pattern profile improvement", etc.

[0012] As described in the above patent, in order to improve resolution and sensitivity, KrF to i-Line photoresists mainly use polyhydroxystyrene and polystyrene polymers with good transmittance at wavelengths of 248nm to 365nm as basic polymers.

[0013] This positive photoresist based on polyhydroxystyrene and polystyrene polymer has difficulties in being used in processes based on 248nm to 365nm light sources due to its sloped pattern or footing development, and as the thickness of the photoresist increases, the achievable resolution decreases. Depending on the type of the underlying film, process problems such as pattern collapse due to problems such as insufficient adhesion have become important issues. Summary of the invention

[0014] Technical issues to be solved

[0015] The object of the present invention is to provide a photoresist composition for KrF to i-Line light sources, which improves the pattern profile and does not cause pattern collapse compared to the existing KrF to i-Line positive photoresist by adding an appropriate amount of a polyhydric alcohol additive that is effective in improving the pattern profile and enhancing the adhesion between the pattern and the underlying film, thereby improving the process margin.

[0016] That is, the purpose is to provide a photoresist composition for KrF to i-Line light sources, which can ensure a vertical profile to improve the pattern profile and ensure stable adhesion between the pattern and the underlying film without causing pattern collapse.

[0017] Technical solutions to the problem

[0018] In order to achieve the above-mentioned object, the present invention provides a positive photoresist composition for KrF to i-Line light sources, which comprises a polyhydric alcohol additive having a molecular weight of 100 to 200 represented by the following chemical formulas 1 to 8, and is used to enhance the adhesion between the chemically amplified resist pattern and the underlying film.

[0019] [Chemical formula 1]

[0020]

[0021] [Chemical formula 2]

[0022]

[0023] [Chemical formula 3]

[0024]

[0025] [Chemical formula 4]

[0026]

[0027] [Chemical formula 5]

[0028]

[0029] [Chemical formula 6]

[0030]

[0031] [Chemical formula 7]

[0032]

[0033] [Chemical formula 8]

[0034]

[0035] In a preferred embodiment of the present invention, the polyhydric alcohol additive and similar structures represented by the above chemical formula for enhancing the adhesion between the resist pattern and the underlying film can be purchased from multiple domestic and foreign suppliers.

[0036] In a preferred embodiment of the present invention, the molecular weight of the polyhydric alcohol additive represented by the above chemical formula for enhancing the adhesion between the resist pattern and the underlying film is 100 to 200.

[0037] In a preferred embodiment of the present invention, it is characterized in that, relative to the total weight of the composition, the polyhydric alcohol additive for enhancing the adhesion between the resist pattern and the underlying film comprises: 5 to 60 wt % of a polymer resin, 1 to 5 wt % of a polyhydric alcohol additive for enhancing the adhesion between the pattern and the underlying film represented by Chemical Formula 1 to Chemical Formula 8, 0.05 to 10 wt % of a photoacid generator, 0.01 to 5 wt % of an acid diffusion inhibitor, and the remainder of a solvent.

[0038] In a preferred embodiment of the present invention, the polymer resin may be any commonly used photoresist resin, and may be one or more selected from the group consisting of the following phenol polymer resins containing hydroxyl groups, chemical formula 9 to chemical formula 13.

[0039] [Chemical formula 9]

[0040]

[0041] In the above structure, R 4 It is a structure selected from the following chemical formula a to chemical formula p.

[0042] <Chemical formula a>

[0043]

[0044] <Chemical formula b>

[0045]

[0046] <Chemical formula c>

[0047]

[0048] <Chemical formula d>

[0049]

[0050] <Chemical formula e>

[0051]

[0052] <Chemical formula f>

[0053]

[0054] <Chemical formula g>

[0055]

[0056] <Chemical formula h>

[0057]

[0058] <Chemical formula i>

[0059]

[0060] <Chemical formula j>

[0061]

[0062] <Chemical formula k>

[0063]

[0064] <Chemical Formula 1>

[0065]

[0066] <Chemical formula m>

[0067]

[0068] <Chemical formula n>

[0069]

[0070] <Chemical formula o>

[0071]

[0072] <Chemical formula>

[0073]

[0074] [Chemical formula 10]

[0075]

[0076] In the above structure, R 5 It is a structure selected from the structures of Chemical Formula a to Chemical Formula p.

[0077] [Chemical formula 11]

[0078]

[0079] In the above structure, R 6 and R 7 Each of them is a structure selected from the structures of Chemical Formula a to Chemical Formula p.

[0080] [Chemical formula 12]

[0081]

[0082] In the above structure, R 8 , R 9 Each of them is a structure selected from the structures of Chemical Formula a to Chemical Formula p.

[0083] [Chemical formula 13]

[0084]

[0085] In the above structure, R 10 , R 11 , R 12 Each of them is a structure selected from the structures of Chemical Formula a to Chemical Formula p.

[0086] In a preferred embodiment of the present invention, the phenol polymer resin is one or more selected from the group consisting of the following phenol polymer resins containing hydroxyl groups represented by Chemical Formula 9 to Chemical Formula 13.

[0087] In a preferred embodiment of the present invention, the photoacid generator is characterized in that the photoacid generator comprises a member selected from the group consisting of triphenylsulfonium triflate, triphenylsulfonium antimonate, diphenyliodonium triflate, diphenyliodonium antimonate, methoxydiphenyliodonium triflate, di-t-buthyldiphenyliodonium triflate, norbornenedicarboxyimide triflate, triphenylsulfonium nonaflate, diphenyliodonium nonaflate, methoxydiphenyliodonium triflate, di-t-butyldiphenyliodonium triflate, norbornenedicarboxyimide triflate, triphenylsulfonium nonaflate, diphenyliodonium nonaflate, and methoxydiphenyliodonium perfluorobutyl sulfonate. phenyliodoniumnonaflate), Di-t-butyldiphenyliodoniumnonaflate, N-hydroxysuccinimidenonaflate, Norbornenedicarboxyimidenonaflate, Triphenylsulfoniumperfluorooctanesulfonate, Diphenyliodoniumperfluorooctanesulfonate, Methoxydiphenyliodoniumperfluorooctanesulfonate One or more selected from the group consisting of diphenyliodoniumperfluorooctanesulfonate, di-t-butyldiphenyliodoniumnonaflate, N-hydroxysuccinimideperfluorooctanesulfonate and norbornenedicarboxyimideperfluorooctanesulfonate.

[0088] In a preferred embodiment of the present invention, the acid diffusion inhibitor includes one or more selected from the group consisting of dimethylamine, diethylamine, trimethylamine, triethylamine, tributhylamine, dimethanolamine, diethanolamine, trimethanolamine, triethanolamine and tributhanolamine.

[0089] Effects of the Invention

[0090] The effect of the present invention is that, by adding an appropriate amount of a polyhydric alcohol additive that is effective in improving the pattern profile and enhancing the adhesion between the pattern and the underlying film, the pattern profile is improved without causing pattern collapse compared to the existing KrF to i-Line positive photoresists, thereby providing a KrF and i-Line light source photoresist composition that can improve the process margin.

[0091] That is, the effect is that a vertical profile can be ensured to improve the pattern profile, and stable adhesion between the pattern and the underlying film can be ensured, thereby providing a photoresist composition for KrF and i-Line light sources that does not cause pattern collapse. DETAILED DESCRIPTION

[0092] Best Mode for Carrying Out the Invention

[0093] Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as those commonly understood by those of ordinary skill in the art to which the invention belongs. Generally, the nomenclature used in this specification is well known and commonly used in the art.

[0094] Throughout the specification of the present invention, when a certain part is referred to as “comprising” a certain constituent element, this means that other constituent elements are not excluded and other constituent elements can be included unless there are special descriptions to the contrary.

[0095] The "polyhydric alcohol additive for enhancing the adhesion between the pattern and the underlying film" proposed in the present invention refers to an additive that can improve the adhesion by reacting with the underlying film during the thermal decomposition process during the PEB (Post Exposed Bake) or HB (Hard Bake) process performed after exposure to a 248nm to 365nm light source.

[0096] In the present invention, the so-called "photoresist" refers to a mixture of a polymer and a photosensitizer, whose chemical properties change due to light. When exposed to light of a certain wavelength, its solubility in a specific solvent changes, resulting in a difference in the dissolution rate of the exposed part and the non-exposed part of the solvent. When the specified dissolution time has passed, an incompletely dissolved part remains to form a pattern.

[0097] In the present invention, "photolithographic process" refers to using the properties of the photoresist as described above to place a mask engraved with a semiconductor design drawing between a light source and a photoresist film coated on a silicon wafer. When the light source is turned on, the circuit engraved on the mask will be transferred to the photoresist as it is.

[0098] In the present invention, "KrF" refers to a light source having a wavelength of 248 nm, and "i-Line" refers to a light source having a wavelength of 365 nm.

[0099] One embodiment of the present invention provides a chemically amplified positive photoresist composition for improving pattern profile and enhancing adhesion, which is characterized by comprising a polyhydric alcohol additive represented by the following chemical formula 1 for enhancing adhesion between the pattern and the underlying film.

[0100] [Chemical formula 1]

[0101]

[0102] [Chemical formula 2]

[0103]

[0104] [Chemical formula 3]

[0105]

[0106] [Chemical formula 4]

[0107]

[0108] [Chemical formula 5]

[0109]

[0110] [Chemical formula 6]

[0111]

[0112] [Chemical formula 7]

[0113]

[0114] [Chemical formula 8]

[0115]

[0116] According to the present invention, a positive photoresist composition for improving pattern profile and enhancing adhesion includes a polyhydric alcohol additive for enhancing adhesion between a pattern and a lower film. The composition may include, relative to the total weight of the composition, 5 to 60 wt % of a polymer resin, 1 to 5 wt % of a polyhydric alcohol additive for enhancing adhesion between a pattern and a lower film represented by Chemical Formula 1 to Chemical Formula 8, 0.05 to 10 wt % of a photoacid generator, 0.01 to 5 wt % of an acid diffusion inhibitor, and the remainder of a solvent.

[0117] Preferably, the polyhydric alcohol additive for enhancing the adhesion between the pattern and the lower film represented by Chemical Formula 1 to Chemical Formula 8 comprises 1 to 5 wt % relative to the total weight of the composition. If the above compound is used in a manner of less than 0.1 wt %, the amount of the polyhydric alcohol additive for enhancing the adhesion between the pattern and the lower film is too small, so the vertical profile cannot be ensured and the pattern collapse problem occurs, and thus there is no effect on improving the adhesion, and when it is used in a manner of more than 5 wt %, although the vertical profile can be ensured without the pattern collapse problem, it will become a cause of other process margins such as slow sensitivity, etc., so it is not preferred.

[0118] The polymer resin may be any commonly used photoresist resin, characterized by being selected from at least one of the following phenol polymer resins containing a hydroxyl group, represented by Chemical Formula 9 to Chemical Formula 13.

[0119] [Chemical formula 9]

[0120]

[0121] In the above structure, R 4 It is a structure selected from the structures of Chemical Formula a to Chemical Formula p.

[0122] <Chemical formula a>

[0123]

[0124] <Chemical formula b>

[0125]

[0126] <Chemical formula c>

[0127]

[0128] <Chemical formula d>

[0129]

[0130] <Chemical formula e>

[0131]

[0132] <Chemical formula f>

[0133]

[0134] <Chemical formula g>

[0135]

[0136] <Chemical formula h>

[0137]

[0138] <Chemical formula i>

[0139]

[0140] <Chemical formula j>

[0141]

[0142] <Chemical formula k>

[0143]

[0144] <Chemical Formula 1>

[0145]

[0146] <Chemical formula m>

[0147]

[0148] <Chemical formula n>

[0149]

[0150] <Chemical formula o>

[0151]

[0152] <Chemical formula>

[0153]

[0154] [Chemical formula 10]

[0155]

[0156] In the above structure, R 5 It is a structure selected from the structures of Chemical Formula a to Chemical Formula p.

[0157] [Chemical formula 11]

[0158]

[0159] In the above structure, R 6 and R 7 Each of them is a structure selected from the structures of Chemical Formula a to Chemical Formula p.

[0160] [Chemical formula 12]

[0161]

[0162] In the above structure, R 8 , R 9 Each of them is a structure selected from the structures of Chemical Formula a to Chemical Formula p.

[0163] [Chemical formula 13]

[0164]

[0165] In the above structure, R 10 , R 11 , R 12 Each of them is a structure selected from the structures of Chemical Formula a to Chemical Formula p.

[0166] In a preferred embodiment of the present invention, the phenol polymer resin is one or more selected from the group consisting of the following phenol polymer resins containing hydroxyl groups represented by Chemical Formula 9 to Chemical Formula 13.

[0167] Preferably, the polymer resin comprises 5 to 60 wt % of the polymer resin relative to the total weight of the composition. If the polymer resin is used in an amount less than 5 wt %, problems such as poor profile, scum, and poor etching resistance may occur, and if the polymer resin is used in an amount exceeding 60 wt %, problems such as poor patterning may occur due to insufficient development.

[0168] The photoacid generator may include a photoacid generator selected from the group consisting of triphenylsulfonium triflate, triphenylsulfonium antimonate, diphenyliodonium triflate, diphenyliodonium antimonate, methoxydiphenyliodonium triflate, di-tert-butyldiphenyliodonium triflate, and di-tert-butyldiphenyliodonium triflate. -t-buthyldiphenyliodoniumtriflate、Norbornenedicarboxyimidetriflate、Triphenylsulfoniumnonaflate、Diphenyliodoniumnonaflate、Methoxydiphenyliodoniumnonaflate、Di-tert-butyldiphenyliodoniumnonaflate Di-t-buthyldiphenyliodoniumnonaflate), N-hydroxysuccinimidenonaflate, Norbornenedicarboxyimidenonaflate, Triphenylsulfoniumperfluorooctanesulfonate, Diphenyliodoniumperfluorooctanesulfonate, Methoxydiphenyliodoniumperfluorooctanesulfonate, Methoxydiphenyliodoniumperfluorooctanesulfonate, N-hydroxysuccinimideperfluorooctanesulfonate, Norbornenedicarboxyimidenonaflate, Triphenylsulfoniumperfluorooctanesulfonate, Diphenyliodoniumperfluorooctanesulfonate, Methoxydiphenyliodoniumperfluorooctanesulfonate, Di-tert-butyldiphenyliodoniumperfluorooctanesulfonate, N-hydroxysuccinimideperfluorooctanesulfonate, Norbornenedicarboxyimidenonaflate, Triphenylsulfoniumperfluorooctanesulfonate, Diphenyliodoniumperfluorooctanesulfonate, Methoxydiphenyliodoniumperfluorooctanesulfonate, At least one selected from the group consisting of nenedicarboxyimideperfluorooctanesulfonate.

[0169] Preferably, the photoacid generator comprises 0.05 to 10 wt % relative to the total weight of the composition. If the photoacid generator is used in an amount less than 0.05 wt %, the pattern tilt surface becomes serious due to insufficient acid generated, and when the amount exceeds 10 wt %, the photoacid generator absorbs light from the exposure source and reduces transmittance, thereby causing pattern defects such as failure to define.

[0170] The acid diffusion inhibitor may include one or more selected from the group consisting of dimethylamine, diethylamine, trimethylamine, triethylamine, tributhylamine, dimethanolamine, diethanolamine, trimethanolamine, triethanolamine and tributhanolamine.

[0171] Preferably, the acid diffusion inhibitor comprises 0.01 to 5 wt % relative to the total weight of the composition. If the acid diffusion inhibitor is used in an amount less than 0.01 wt %, pattern defects such as poor pattern formation (line width roughness (LWR), line edge roughness (LER)) of the pattern wall or edge portion may occur due to excessive acid generation, and when it is greater than 5 wt %, there is a problem that a pattern cannot be formed.

[0172] On the other hand, the thickness of the chemically amplified positive photoresist composition for improving pattern profile and enhancing adhesion, which contains the polyhydric alcohol additive for enhancing the adhesion between the pattern and the underlying film of the present invention, can be adjusted according to the type and amount of the solvent used. to It can be used after being dissolved in 10 to 90% by weight relative to the weight of the solvent.

[0173] As the solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, diethylene glycol dimethyl ether, ethyl lactate, toluene, xylene, methyl ethyl ketone, cyclohexanone, 2-heptanoin ne), 3-heptanone (3-heptanone), 4-heptanone (4-heptanone), etc., and can be used alone or in combination.

[0174] As described above, the chemically amplified positive photoresist composition provided by the present invention includes a polyhydric alcohol additive for enhancing the adhesion between the pattern and the underlying film to improve the pattern profile and enhance the adhesion. The polyhydric alcohol additive for enhancing the adhesion between the pattern and the underlying film represented by Chemical Formula 1 to Chemical Formula 8 can obtain a vertical profile according to the exposure energy and has the effect of enhancing the adhesion, thereby providing a process margin compared to the existing KrF to i-Line PR.

[0175] Specific ways to implement the invention

[0176] Example

[0177] The present invention is described in more detail below by way of examples. These examples are only used to illustrate the present invention and are not to be construed as limiting the scope of the present invention based on these examples, which is obvious to those skilled in the art to which the present invention belongs.

[0178] Example 1

[0179] A phenol polymer resin having a weight average molecular weight of 15,000 (in Chemical Formula 12, R 8 Is the chemical formula a, R 9 A KrF excimer laser positive photoresist composition was prepared by using a mixed solution of 106.0 g of propylene glycol monomethyl ether and 106.0 g of propylene glycol methyl ether acetate as a solvent. The prepared composition was coated on a silicon wafer coated with aluminum (Al) using a spin coater, and after soft baking at 100°C for 120 seconds, the target thickness of 5 μm was confirmed. The exposure process was completed under a 248nm light source, followed by a baking process (PEB) at 120°C for 90 seconds, and then a development process using 2.38% tetramethylammonium hydroxide was performed to form a pattern. As a result, it was confirmed that the sensitivity was 118mJ / cm 2 , a pattern slope with a line / space standard resolution of 3.0 μm and a positive slope pattern with a slope angle of 84.3° were confirmed, and no pattern collapse was confirmed.

[0180] Example 2

[0181] A phenol polymer resin having a weight average molecular weight of 15,000 (in Chemical Formula 12, R 8 Is the chemical formula a, R 9A KrF excimer laser positive photoresist composition was prepared by using a mixed solution of 107.5 g of propylene glycol monomethyl ether and 107.5 g of propylene glycol methyl ether acetate as a solvent. The prepared composition was coated on a silicon wafer coated with aluminum (Al) using a spin coater, and after soft baking at 100°C for 120 seconds, the target thickness of 5 um was confirmed. The pattern was formed by performing an exposure process under a 248 nm light source, a baking process (PEB) at 120°C for 90 seconds, and a development process using 2.38% tetramethylammonium hydroxide. As a result, the sensitivity was confirmed to be 117 mJ / cm 2 , a pattern slope with a line / space standard resolution of 2.8 μm and a positive slope pattern with a slope angle of 84.9° were confirmed, and no pattern collapse was confirmed.

[0182] Example 3

[0183] A phenol polymer resin having a weight average molecular weight of 15,000 (in Chemical Formula 12, R 8 Is the chemical formula a, R 9 A KrF excimer laser positive photoresist composition was prepared by using a mixed solution of 110.0 g of propylene glycol monomethyl ether and 110.0 g of propylene glycol methyl ether acetate as a solvent. The prepared composition was coated on a silicon wafer coated with aluminum (Al) using a spin coater, and after soft baking at 100°C for 120 seconds, the target thickness of 5 μm was confirmed. The pattern was formed by performing an exposure process under a 248 nm light source, a baking process (PEB) at 120°C for 90 seconds, and a development process using 2.38% tetramethylammonium hydroxide. As a result, it was confirmed that the sensitivity was 115 mJ / cm 2, a pattern slope with a line / space standard resolution of 2.8 μm and a positive slope pattern with a slope angle of 85.4° were confirmed, and no pattern collapse was confirmed.

[0184] Example 4

[0185] A phenol polymer resin having a weight average molecular weight of 15,000 (in Chemical Formula 12, R 8 Is the chemical formula a, R 9 A KrF excimer laser positive photoresist composition was prepared by using a mixed solution of 112.5 g of propylene glycol monomethyl ether and 112.5 g of propylene glycol methyl ether acetate as a solvent. The prepared composition was coated on a silicon wafer coated with aluminum (Al) using a spin coater, and after soft baking at 100°C for 120 seconds, the target thickness of 5 um was confirmed. The exposure process was completed under a 248nm light source, followed by a baking process (PEB) at 120°C for 90 seconds, and then a development process using 2.38% tetramethylammonium hydroxide was performed to form a pattern. As a result, it was confirmed that the sensitivity was 112mJ / cm 2 , a pattern slope with a line / space standard resolution of 2.5 μm and a positive slope pattern with a slope angle of 88.8° were confirmed, and no pattern collapse was confirmed.

[0186] Example 5

[0187] A phenol polymer resin having a weight average molecular weight of 15,000 (in Chemical Formula 12, R 8 Is the chemical formula a, R 9A KrF excimer laser positive photoresist composition was prepared by using a mixed solution of 115.0 g of propylene glycol monomethyl ether and 115.0 g of propylene glycol methyl ether acetate as a solvent. The prepared composition was coated on a silicon wafer coated with aluminum (Al) using a spin coater, and after soft baking at 100°C for 120 seconds, the target thickness of 5 μm was confirmed. The pattern was formed by performing an exposure process under a 248 nm light source, a baking process (PEB) at 120°C for 90 seconds, and a development process using 2.38% tetramethylammonium hydroxide. As a result, it was confirmed that the sensitivity was 110 mJ / cm 2 , a pattern slope with a line / space standard resolution of 2.4 μm and a positive slope pattern with a slope angle of 89.2° were confirmed, and no pattern collapse was confirmed.

[0188] Example 6

[0189] A phenol polymer resin having a weight average molecular weight of 15,000 (in Chemical Formula 12, R 8 Is the chemical formula a, R 9 A KrF excimer laser positive photoresist composition was prepared by using a mixed solution of 115.5 g of propylene glycol monomethyl ether and 115.5 g of propylene glycol methyl ether acetate as a solvent. The prepared composition was coated on a silicon wafer coated with aluminum (Al) using a spin coater, and after soft baking at 100°C for 120 seconds, the target thickness of 5 um was confirmed. The pattern was formed by performing an exposure process under a 248 nm light source, a baking process (PEB) at 120°C for 90 seconds, and a development process using 2.38% tetramethylammonium hydroxide. As a result, the sensitivity was confirmed to be 109 mJ / cm 2, a fine negative slope pattern with a line / space standard resolution of 2.4μm and a slope angle of 91.9° was confirmed, and no pattern collapse was confirmed.

[0190] Example 7

[0191] A phenol polymer resin having a weight average molecular weight of 15,000 (in Chemical Formula 12, R 8 Is the chemical formula a, R 9 A KrF excimer laser positive photoresist composition was prepared by using a mixed solution of 116.5 g of propylene glycol monomethyl ether and 116.5 g of propylene glycol methyl ether acetate as a solvent. The prepared composition was coated on a silicon wafer coated with aluminum (Al) using a spin coater, and after soft baking at 100°C for 120 seconds, the target thickness of 5 um was confirmed. The pattern was formed by performing an exposure process under a 248 nm light source, a baking process (PEB) at 120°C for 90 seconds, and a development process using 2.38% tetramethylammonium hydroxide. As a result, the sensitivity was confirmed to be 107 mJ / cm 2 , a fine negative slope pattern with a line / space standard resolution of 2.3 μm and a slope angle of 92.2° was confirmed, and no pattern collapse was confirmed.

[0192] Example 8

[0193] A phenol polymer resin having a weight average molecular weight of 15,000 (in Chemical Formula 12, R 8 Is the chemical formula a, R 9A KrF excimer laser positive photoresist composition was prepared by using a mixed solution of 118.0 g of propylene glycol monomethyl ether and 118.0 g of propylene glycol methyl ether acetate as a solvent. The prepared composition was coated on a silicon wafer coated with aluminum (Al) using a spin coater, and after soft baking at 100°C for 120 seconds, the target thickness of 5 μm was confirmed. The pattern was formed by performing an exposure process under a 248 nm light source, a baking process (PEB) at 120°C for 90 seconds, and a development process using 2.38% tetramethylammonium hydroxide. As a result, it was confirmed that the sensitivity was 105 mJ / cm 2 , a fine negative slope pattern with a line / space standard resolution of 2.3 μm and a slope angle of 94.8° was confirmed, and no pattern collapse was confirmed.

[0194] Example 9

[0195] A phenol polymer resin having a weight average molecular weight of 15,000 (in Chemical Formula 12, R 8 Is the chemical formula a, R 9 A KrF excimer laser positive photoresist composition was prepared by using a mixed solution of 119.0 g of propylene glycol monomethyl ether and 119.0 g of propylene glycol methyl ether acetate as a solvent. The prepared composition was coated on a silicon wafer coated with aluminum (Al) using a spin coater, and after soft baking at 100°C for 120 seconds, the target thickness of 5 μm was confirmed. The pattern was formed by performing an exposure process under a 248 nm light source, performing a baking process (PEB) at 120°C for 90 seconds, and then performing a development process using 2.38% tetramethylammonium hydroxide. As a result, it was confirmed that the sensitivity was 104 mJ / cm 2, a fine negative slope pattern with a line / space standard resolution of 2.3 μm and a slope angle of 95.1° was confirmed, and no pattern collapse was confirmed.

[0196] Comparative Example 1

[0197] The experiment was conducted in the same manner as in Example 1 except that the polyhydric alcohol additive for enhancing the adhesion between the pattern and the lower film was not added. As a result, it was confirmed that the sensitivity was 125 mJ / cm 2 , a pattern with a line / space standard resolution of 3.5 μm could be confirmed, but pattern collapse (Pattern Collaps) was confirmed.

[0198] Comparative Example 2

[0199] A phenol polymer resin having a weight average molecular weight of 15,000 (in Chemical Formula 12, R 8 Is the chemical formula a, R 9 A KrF excimer laser positive photoresist composition was prepared by using a mixed solution of 105.0 g of propylene glycol monomethyl ether and 105.0 g of propylene glycol methyl ether acetate as a solvent. The prepared composition was coated on a silicon wafer coated with aluminum (Al) using a spin coater, and after soft baking at 100°C for 120 seconds, the target thickness of 5 μm was confirmed. The pattern was formed by performing an exposure process under a 248 nm light source, a baking process (PEB) at 120°C for 90 seconds, and a development process using 2.38% tetramethylammonium hydroxide. As a result, it was confirmed that the sensitivity was 120 mJ / cm 2 , a pattern with a line / space standard resolution of 3.0 μm could be confirmed, but pattern collapse (Pattern Collaps) was confirmed.

[0200] Comparative Example 3

[0201] A phenol polymer resin having a weight average molecular weight of 15,000 (in Chemical Formula 12, R 8Is the chemical formula a, R 9 A KrF excimer laser positive photoresist composition was prepared by using a mixed solution of 119.5 g of propylene glycol monomethyl ether and 119.5 g of propylene glycol methyl ether acetate as a solvent. The prepared composition was coated on a silicon wafer coated with aluminum (Al) using a spin coater, and after soft baking at 100°C for 120 seconds, the target thickness of 5 μm was confirmed. The exposure process was completed under a 248nm light source, followed by a baking process (PEB) at 120°C for 90 seconds, and then a development process using 2.38% tetramethylammonium hydroxide was performed to form a pattern. As a result, it was confirmed that the sensitivity was 101mJ / cm 2 , a fine negative slope pattern with a line / space standard resolution of 2.2μm and a slope angle of 96.6° was confirmed, and no pattern collapse was confirmed.

[0202] Characteristic determination

[0203] The chemically amplified positive photoresist compositions prepared as described in Examples 1 to 5 and Comparative Example 1 for improving pattern profile and enhancing adhesion were characterized.

[0204] Resolution and adhesion were measured using a critical dimension scanning electron microscope (CD-SEM) that can observe the line width of the pattern, and the minimum line width (resolution) was observed and confirmed based on L / S (Line / Space). In addition, for sensitivity, the energy (Energy) that can determine the minimum line width (resolution) was measured as the sensitivity.

[0205] The results of the above measurements are shown in Table 1 below.

[0206] [Table 1]

[0207]

[0208] From the above and Table 1, it can be confirmed that, based on the evaluation results of adding a polyhydric alcohol additive for enhancing the adhesion between the pattern and the lower film, the sensitivity of Examples 1 to 9 is improved compared to Comparative Examples 1 and 2, and the resolution as the minimum line width is also improved. In addition, it is confirmed that the vertical pattern slope is also improved.

[0209] When the content of the polyhydric alcohol additive used to enhance the adhesion between the pattern and the lower film in the embodiment is 1 to 5 weight %, it is confirmed that the sensitivity, resolution and pattern angle show excellent results. In particular, when the content is 2.9 to 4.0 weight % as in Examples 4 to 7, it is confirmed that the sensitivity, resolution and pattern angle show excellent results. The results confirmed by using a scanning electron microscope (CD-SEM) for critical dimension measurement show that, although the sensitivity and resolution as the minimum line width size are improved in Comparative Examples 2 and 3 compared with Comparative Example 1, pattern collapse is confirmed in some areas.

[0210] Simple modifications or changes of the present invention can be easily realized by ordinary technicians in the technical field to which the present invention belongs, and it can be considered that such modifications or changes are included in the scope of the present invention.

Claims

1. A chemically amplified positive photoresist composition for improving pattern profile and enhancing adhesion, which is a photoresist composition capable of being exposed using a light source with a wavelength of 248 nm, characterized in that: In order to realize a vertical profile without pattern collapse, 1 to 5 wt % of a polyol additive represented by the following Chemical Formula 1 to Chemical Formula 8 is included, [Chemical formula 1] [Chemical formula 2] [Chemical formula 3] [Chemical formula 4] [Chemical formula 5] [Chemical formula 6] [Chemical formula 7] [Chemical formula 8] 2. The chemically amplified positive photoresist composition for improving pattern profile and enhancing adhesion according to claim 1, characterized in that: The photoresist composition comprises, relative to the total weight of the composition, 5 to 60 wt % of a polymer resin, 1 to 5 wt % of a polyol additive represented by Chemical Formula 1 to Chemical Formula 8, 0.05 to 10 wt % of a photoacid generator, 0.01 to 5 wt % of an acid diffusion inhibitor, and the remainder of a solvent.

3. The chemically amplified positive photoresist composition for improving pattern profile and enhancing adhesion according to claim 2, characterized in that: The polymer resin is one or more selected from the following phenolic polymer resins containing hydroxyl groups, Chemical Formula 9 to Chemical Formula 13, [Chemical formula 9] In the above structure, R4 is a structure selected from the following chemical formula a to chemical formula p: <Chemical formula b> <Chemical formula c> <Chemical formula d> <Chemical formula e> <Chemical formula f> <Chemical formula g> <Chemical formula h> <Chemical formula i> <Chemical formula j> <Chemical formula k> <Chemical Formula 1> <Chemical formula m> <Chemical formula n> <Chemical formula o> <Chemical formula> [Chemical formula 10] In the above structure, R5 is a structure selected from the structures of chemical formula a to chemical formula p, [Chemical formula 11] In the above structure, R6 and R7 are each selected from a structure of chemical formula a to chemical formula p. [Chemical formula 12] In the above structure, R8 and R9 are respectively selected from one structure of chemical formula a to chemical formula p. [Chemical formula 13] In the above structure, R 10 , R 11 , R 12 Each of them is a structure selected from the structures of Chemical Formula a to Chemical Formula p.

4. The chemically amplified positive photoresist composition for improving pattern profile and enhancing adhesion according to claim 2, characterized in that: The photoacid generator comprises a triphenylsulfonium triflate, a triphenylsulfonium antimonate, a diphenyliodonium triflate, a diphenyliodonium antimonate, a methoxydiphenyliodonium triflate, a di-t-butyldiphenyliodonium triflate, a 2,6-dinitrobenzenesulfonate ...6-dinitrobenzylsulponate), pyrogalloltrisalkylsulfonate, norbornenedicarboxyimidetriflate, triphenylsulfoniumnonaflate, diphenyliodoniumnonaflate, methoxydiphenyliodoniumnonaflate, di-t-butyldiphenyliodoniu mnonaflate, N-hydroxysuccinimidonenonaflate, norbornenedicarboxyimidetriflate, triphenylsulfoniumnonaflate, diphenyliodoniumnonaflate, methoxydiphenyliodoniumnonaflate, di-t-butyldiphenyliodoniu mnonaflate, N-hydroxysuccinimidonenonaflate, norbornenedicarboxyimidetriflate, triphenylsulfoniumnonaflate, diphenyliodoniumnonaflate, methoxydiphenyliodoniumnonaflate, di-t-butyldiphenyliodoniu mnonaflate, denonaflate), triphenylsulfoniumperfluorooctane sulfonate, diphenyliodoniumperfluorooctane sulfonate, methoxydiphenyliodoniumperfluorooctanesulfonate, di-t-buthyldiphenyliodoniumnonaflate, N-hydroxysuccinimideperfluorooctanesulfonate and norbornenedicarboxyimideperfluorooctanesulfonate.

5. The chemically amplified positive photoresist composition for improving pattern profile and enhancing adhesion according to claim 2, characterized in that: The acid diffusion inhibitor includes at least one selected from the group consisting of dimethylamine, diethylamine, trimethylamine, triethylamine, tributylamine, dimethanolamine, diethanolamine, trimethanolamine, triethanolamine, and tributanolamine.

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