Method for forming a photoresist pattern and semiconductor device manufactured using the same

Abstract

The present invention aims to provide a method for forming a photoresist pattern that can improve defects such as pattern collapse during the spin-drying process after washing with ultrapure water and / or rinsing solution when forming a pattern with an increased aspect ratio using conventional photoresists, and to provide a semiconductor device with improved performance manufactured using the photoresist pattern formation method. [Solution] The present invention relates to a method for forming a photoresist pattern with an increased aspect ratio using conventional photoresists, and to a semiconductor device manufactured using the same. By using heated ultrapure water and / or rinsing solution in the cleaning stage, it is possible to improve the occurrence of defects in which the pattern collapses during the spin-drying process after cleaning, thereby increasing the overall process yield, and providing a semiconductor device exhibiting improved performance using the method.

Description

Technical Field

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

Background Art

[0002] During the semiconductor manufacturing process, in the photolithography process using photoresist, the critical dimension (CD) of the pattern is affected by the diffraction characteristics of the light source irradiated. In order to improve the performance of the semiconductor, it is important to implement a smaller line width to increase the integration degree. In order to form a finer pattern in the exposure stage, KrF light sources and ArF light sources have been used, and currently, photolithography technology using an extreme ultraviolet (EUV, 13.5 nm) light source has been adopted so that a finer line width can be implemented.

[0003] On the other hand, due to the fact that the etching resistance of the photoresist for extreme ultraviolet is still not sufficient, in order to form a fine pattern, it is necessary to reduce the line width of the pattern and to form it to a certain thickness or more in order to prevent defects in the etching process. Thus, a photoresist pattern with an increased aspect ratio is required for forming a fine pattern. However, as the aspect ratio of the pattern increases, there is a problem that the process margin is greatly reduced because defects in which the pattern collapses are likely to occur in the development and cleaning processes after exposure.

[0004] In order to improve such defects in which the pattern collapses, research on improving the physical properties of the photoresist for extreme ultraviolet has been continued, but it is impossible to ignore the fact that it is difficult to newly develop a photoresist that satisfies all various physical properties.

[0005] In this regard, Korean Patent Publication No. 10-2015-0093098 discloses a method for cleaning patterns using a cleaning solution containing a fluorine-based compound. However, in recent years, with the formation of patterns with increasingly larger aspect ratios, problems such as pattern collapse and watermarks due to insufficient drying of the cleaning solution have been reported.

[0006] Therefore, there is a need to develop a novel method for forming photoresist patterns that can improve the defect of the pattern collapsing when forming patterns with increased aspect ratios. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Korean Published Patent Gazette No. 10-2015-0093098 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] To solve the above-mentioned problems, the present invention aims to provide a method for forming a photoresist pattern that can improve the defect of the pattern collapsing during the spin-drying process after washing with ultrapure water and / or rinsing solution when forming a pattern with an increased aspect ratio using conventional photoresists.

[0009] Furthermore, the present invention aims to provide a semiconductor device having improved performance, manufactured using the photoresist pattern formation method described above.

[0010] However, the problems that this invention aims to solve are not limited to those mentioned above, and other problems not mentioned will be clearly understood by an ordinary person from the following description. [Means for solving the problem]

[0011] To achieve the above objective, the present invention provides a method for forming a photoresist pattern, comprising the steps of (a) applying a photoresist composition to a substrate to form a photoresist film; (b) exposure step of irradiating the formed photoresist film with light; (c) developing the exposed photoresist film with a developer; and (d) washing the developed photoresist film, wherein step (d) sequentially includes an ultrapure water washing step and a rinse solution washing step, and at least one of the ultrapure water and rinse solution in step (d) is sprayed at a temperature of 30°C to 90°C.

[0012] In the method for forming the pattern described above, at least one of the ultrapure water and rinsing solution in step (d) may be sprayed at a temperature of 50°C to 80°C.

[0013] In the method for forming the pattern described above, at least one of the ultrapure water and rinsing solution in step (d) may be sprayed at a temperature of 65°C to 75°C.

[0014] In the method for forming the pattern described above, the ultrapure water washing step may involve spraying ultrapure water onto a substrate rotating at a speed of 1 rpm to 2,000 rpm at a flow rate of 1 ml / min to 2,000 ml / min for 1 second to 300 seconds.

[0015] In the method for forming the pattern described above, the rinse liquid washing step may involve spraying rinse liquid onto a substrate rotating at a speed of 1 rpm to 1,500 rpm at a flow rate of 1 ml / min to 1,000 ml / min for 1 second to 100 seconds.

[0016] In the method for forming the pattern described above, the rinse solution may contain a surfactant, an additive, and water.

[0017] In the method for forming the pattern described above, the rinse solution may contain, with respect to the total weight of the rinse solution, 0.0001% to 1% by weight of a surfactant; 0.0001% to 1% by weight of an additive; and the remainder being water.

[0018] In the above method for forming a pattern, the photoresist pattern can have a line width of 25 nm or less.

[0019] In the above method for forming a pattern, the photoresist pattern can have an aspect ratio (height / line width) of 1.5 or more.

[0020] In the above method for forming a pattern, the exposure light source in step (b) can be any one selected from the group consisting of KrF, ArF, VUV, ArFi, and EUV.

[0021] The present invention also provides a semiconductor device manufactured using the method for forming a photoresist pattern.

Advantages of the Invention

[0022] The method for forming a photoresist pattern according to the present invention uses ultrapure water and / or rinse liquid heated during the cleaning step, and can improve the problem that defects such as pattern collapse occur during the spin-dry process after cleaning, even when forming a pattern with an increased aspect ratio using a conventional photoresist.

[0023] Also, the method for forming a photoresist pattern according to the present invention can prevent defects such as pattern collapse during the cleaning step while enabling the formation of a fine pattern with an increased aspect ratio, thereby increasing the overall process yield, and can also improve the performance of the semiconductor device manufactured thereby.

[0024] In addition, a semiconductor device manufactured using the method for forming a photoresist pattern of the present invention can exhibit improved performance.

Brief Description of the Drawings

[0025] [Figure 1] It is a process diagram roughly showing the development step and the cleaning step of the method for forming a photoresist pattern according to the present invention. [Figure 2] It is a configuration diagram schematically showing track equipment used in a method for forming a photoresist pattern according to the present invention. [Figure 3] It is a diagram showing the result of evaluating a defect in which the pattern of a photoresist pattern formed according to Example 47 of the present invention collapses. [Figure 4] It is a diagram showing the result of evaluating a defect in which the pattern of a photoresist pattern formed according to Comparative Example 1 of the present invention collapses.

Embodiments for Carrying Out the Invention

[0026] The present invention relates to a method for forming a photoresist pattern for forming a pattern having an increased aspect ratio using a conventional photoresist and a semiconductor device manufactured using the same.

[0027] All terms (including technical and scientific terms) used in this specification are used with a meaning commonly understood by those having ordinary knowledge in the technical field to which the present invention pertains, unless otherwise defined. Also, terms defined in commonly used dictionaries should not be interpreted abnormally or excessively, unless specifically defined otherwise.

[0028] Also, as used in this specification, "comprises" and / or "comprising" are used in a sense that does not exclude the presence or addition of one or more other components and / or steps other than the recited components and / or steps.

[0029] Also, in this specification, for the numerical ranges indicated as "a to b" and "a~b", "to" and "~" are defined as being ≧a and ≦b.

[0030] The present invention provides a method for forming a photoresist pattern, comprising the steps of (a) applying a photoresist composition to a substrate to form a photoresist film; (b) exposure step of irradiating the formed photoresist film with light; (c) developing the exposed photoresist film with a developer; and (d) washing the developed photoresist film, wherein step (d) sequentially includes an ultrapure water washing step and a rinse solution washing step, and at least one of the ultrapure water and rinse solution in step (d) is sprayed at a temperature of 30°C to 90°C.

[0031] Furthermore, the present invention provides a semiconductor device manufactured using the photoresist pattern formation method described above.

[0032] The photoresist composition used in step (a) above includes a positive photoresist composition and a negative photoresist composition. In other words, the photoresist composition means a resin composition that can form a film whose solubility in an alkaline developer increases or decreases as a result of a chemical reaction caused by exposure.

[0033] From the viewpoint of forming fine patterns, the photoresist composition is preferably an EUV photoresist composition that uses EUV as an exposure source.

[0034] The substrate used in step (a) above may be, but is not limited to, a glass substrate or a silicon wafer.

[0035] The method for applying the photoresist composition to the substrate in step (a) above can be a method known in the art, and may be applied using a suitable method such as spin coating or slit coating.

[0036] The exposure source in step (b) above may be any one selected from the group consisting of KrF (248 nm), ArF (193 nm), VUV (157 nm), ArFi (38 nm), and EUV (13.5 nm), and it is preferable to use EUV as the exposure source from the viewpoint of forming a fine pattern.

[0037] The method for forming a photoresist pattern of the present invention preferably further includes a soft baking step before step (b) and / or a post-exposure baking (PEB) step after step (b).

[0038] The soft baking step and the post-exposure baking step can each be carried out independently at a temperature of 150°C or lower, preferably at a temperature of 110°C or lower, and more preferably at a temperature of 70°C to 110°C.

[0039] Figure 1 is a schematic process diagram showing the (c) development step and (d) washing step of the photoresist pattern formation method according to the present invention. Referring to Figure 1, the photoresist pattern formation method according to the present invention includes, in order, an ultrapure water washing step and a rinse solution washing step after the development step.

[0040] The developer in step (c) above may be an alkaline developer, and it is preferable that the alkaline developer is an aqueous solution of tetramethylammonium hydroxide (TMAH) in a concentration of 0.01% to 5% by weight.

[0041] For example, development methods such as immersing the substrate in a tank filled with developer for a certain period of time (dipping method), developing by spraying developer onto the surface of the substrate and rotating it at a low speed for a certain period of time (paddle method), or spraying developer onto the surface of the substrate using a spray (spray method) can be applied.

[0042] The (d) step is a step of washing the developed photoresist film, and is characterized by including, in order, an ultrapure water washing step and a rinse solution washing step after the development step.

[0043] The aforementioned ultrapure water washing step may involve spraying ultrapure water onto a substrate rotating at a speed of 1 rpm to 2,000 rpm at a flow rate of 1 ml / min to 2,000 ml / min for 1 second to 300 seconds, in which case the total amount of ultrapure water sprayed may be 100 ml to 5,000 ml.

[0044] The rinse solution cleaning step may involve spraying rinse solution onto a substrate rotating at a speed of 1 rpm to 1,500 rpm at a flow rate of 1 ml / min to 1,000 ml / min for 1 second to 100 seconds, in which case the total amount of rinse solution sprayed may be 1 ml to 300 ml.

[0045] In one embodiment of the present invention, at least one of the ultrapure water and rinsing solution in step (d) may be sprayed at a temperature of 30°C to 90°C, preferably at least one of the ultrapure water and rinsing solution may be sprayed at a temperature of 50°C to 80°C, and more preferably at least one of the ultrapure water and rinsing solution may be sprayed at a temperature of 65°C to 75°C.

[0046] In another embodiment of the present invention, the ultrapure water and rinsing solution in step (d) may both be sprayed at a temperature of 50°C to 80°C, and preferably both the ultrapure water and rinsing solution may be sprayed at a temperature of 65°C to 75°C.

[0047] In yet another embodiment of the present invention, one of the ultrapure water and the rinsing solution in step (d) may be sprayed at a temperature of 65°C to 75°C and the other at a temperature of 30°C to 80°C, and more preferably, one of the ultrapure water and the rinsing solution may be sprayed at a temperature of 65°C to 75°C and the other at a temperature of 50°C to 70°C.

[0048] In yet another embodiment of the present invention, one of the ultrapure water and the rinse solution in step (d) may be sprayed at a temperature of 50°C to 70°C, and the other may be sprayed at a temperature of 60°C to 80°C.

[0049] During the formation of photoresist patterns, aqueous compositions based on ultrapure water are primarily used in the post-development washing stage. However, such aqueous compositions have relatively high surface tension and form a high contact angle with the photoresist. Therefore, when used in the washing stage, there is a problem in that the pattern may collapse due to capillary force.

[0050] The inventors of this invention experimentally confirmed that the phenomenon of patterns collapsing during the formation of fine patterns can be prevented by using ultrapure water and water-based rinsing solutions based on ultrapure water at a temperature higher than room temperature (20°C to 25°C), specifically at a high temperature (30°C to 90°C), thereby completing the present invention.

[0051] As the temperature of the ultrapure water and rinse solution increases, the kinetic energy of water molecules increases, weakening the hydrogen bonds between water molecules and thus reducing the cohesion force between water molecules. This lowers the surface tension, contact angle, and viscosity, and also reduces the capillary force. It is believed that this reduced capillary force prevents defects such as the patterns collapsing as the ultrapure water and rinse solution pass through the fine patterns during the drying process after washing.

[0052] Figure 2 is a schematic diagram showing the track equipment used in the photoresist pattern formation method according to the present invention. The track equipment includes an ultrapure water constant temperature device 100 and a rinse solution constant temperature device 200 for maintaining the ultrapure water and rinse solution used in the cleaning stage at a constant temperature, and includes a process track 300 for spraying the ultrapure water and rinse solution onto the substrate to perform the cleaning stage.

[0053] The ultrapure water constant temperature device 100 and the rinse solution constant temperature device 200 may include a temperature sensing unit (not shown) that senses the temperature of the ultrapure water or rinse solution stored inside, so that the ultrapure water or rinse solution can be maintained at a preset constant temperature.

[0054] The rinsing solution in step (d) comprises a surfactant, an additive, and water, and may further contain a solvent if necessary.

[0055] In one embodiment of the present invention, the rinse solution may consist of a surfactant, an additive, and water.

[0056] The surfactant plays a role in reducing the surface tension of water while simultaneously increasing its surfactant activity, and may include one or more selected from the group consisting of fluorinated surfactants, hydrocarbon surfactants, silicone surfactants, anionic surfactants, and cationic surfactants.

[0057] Examples of the fluorinated surfactants include, but are not limited to, fluorinated acrylic carboxylates, fluorinated alkyl ethers, fluorinated alkyl ethers, fluorinated alkyl sulfates, fluorinated alkyl phosphates, fluorinated acrylic copolymers, fluorinated copolymers, perfluorinated acids, perfluorinated carboxyl salts, and perfluorinated sulfonates.

[0058] Examples of the hydrocarbon-based surfactants include, but are not limited to, polyoxyethylene monomethyl ether, polyoxyethylene monoallyl ether, polyoxyethylene-2-ethylhexyl ether, polyoxyethylene decyl ether, polyoxyethylene isotridecyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene polyoxypropylene tridecyl ether, and polyoxyethylene lauryl ether.

[0059] Examples of the aforementioned silicone-based surfactants include, but are not limited to, poly(dimethylsiloxane) ethoxylate, poly(dimethylsiloxane) ethoxylate / propoxylate copolymer, trimethylsiloxane ethoxylate, and trimethylsiloxane ethoxylate / propoxylate copolymer.

[0060] The aforementioned anionic surfactants include, for example, disodium laureth sulfosuccinate, disodium lauryl sulfosuccinate, disodium cocoyl glutamate, cocoyl glutamate, disodium hydrogeneted tauroyl glutamate, disodium stearoyl glutamate, hydrogeneted tauroyl glutamate, lauroyl glutamate, myristoyl glutamate, palmitoyl glutamate, potassium cocoyl glutamate, potassium lauroyl glutamate. Examples include, but are not limited to, glutamate, potassium myristoyl glutamate, sodium cocoyl glutamate, sodium hydrogenerated talouyl glutamate, sodium lauroyl glutamate, sodium myristoyl glutamate, sodium stearoyl glutamate, stearoyl glutamate, TEA-cocoyl glutamate, TEA-hydrogenerated talouyl glutamate, and TEA-lauroyl glutamate.

[0061] Examples of the cationic surfactants include, but are not limited to, alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, benzalkonium chloride, and stearylamine acetate.

[0062] The surfactant may be present in an amount of 0.0001% to 1% by weight, preferably 0.001% to 0.5% by weight, relative to the total weight of the rinse solution. When the surfactant content is within the above range, it has the advantage of not reducing the cleaning power of the rinse solution while appropriately reducing the surface tension.

[0063] The additive may contain any component as long as it does not significantly impair the effects of the present invention. The additive may include, for example, one or more selected from the group consisting of triol derivatives, tetraol derivatives, antioxidants, corrosion inhibitors, defoamers, rust inhibitors, and preservatives, preferably one or more selected from the group consisting of triol derivatives and tetraol derivatives, and more preferably a triol derivative. The additive may be included in an amount of 0.0001% to 1% by weight, preferably 0.001% to 0.5% by weight, based on the total weight of the rinse solution.

[0064] The aforementioned triol derivatives are compounds having 3 to 10 carbon atoms and possessing three hydroxyl groups (-OH) in the molecule, including 1,2,3-propanetriol, 1,2,4-butanetriol, 1,1,4-butanetriol, 1,3,5-pentanetriol, 1,2,5-pentanetriol, 2,3,4-pentanetriol, 1,2,3-hexanetriol, 1,2,6-hexanetriol, and 1,3,4-hexanetriol. Riol, 1,4,5-hexanetriol, 2,3,4-hexanetriol, 1,2,3-heptanetriol, 1,2,4-heptanetriol, 1,2,6-heptanetriol, 1,3,5-heptanetriol, 1,4,7-heptanetriol, 2,3,4-heptanetriol, 2,4,6-heptanetriol, 1,2,8-octanetriol, 1,3,5-octanetriol, 1, It may be selected from the group consisting of 4,7-octanetriol, butane-1,1,1-triol, 2-methyl-1,2,3-propanetriol, 5-methylhexane-1,2,3-triol, 2,6-dimethyl-3-heptene-2,4,6-triol, benzene-1,3,5-triol, 2-methylbenzene-1,2,3-triol, 5-methylbenzene-1,2,3-triol, 2,4,6-trimethylbenzene-1,3,5-triol, naphthalene-1,4,5-triol, 5,6,7,8-tetrahydronaphthalene-1,6,7-triol, 5-hydromethylbenzene-1,2,3-triol, 5-isopropyl-2-methyl-5-cyclohexene-1,2,4-triol, 4-isopropyl-4-cyclohexene-1,2,3-triol, or mixtures thereof.

[0065] The tetraol derivatives are compounds with 4 to 14 carbon atoms and four hydroxyl groups (-OH) in the molecule, including 1,2,3,4-butanetetraol, 1,2,3,4-pentanetetraol, 1,2,4,5-pentanetetraol, 1,2,3,4-hexanetetraol, 1,2,3,5-hexanetetraol, 1,2,3,6-hexanetetraol, 1,2,4,5-hexanetetraol, 1,2,4,6-hexanetetraol, 1,2,5,6-hexanetetraol, 1,3,4,5-hexanetetraol, 1,3,4,6-hexanetetraol, 2,3,4,5-hexanetetraol, and 1,2,6,7- It may be selected from the group consisting of heptanetetraol, 2,3,4,5-heptanetetraol, 1,1,1,2-octanetetraol, 1,2,7,8-octanetetraol, 1,2,3,8-octanetetraol, 1,3,5,7-octanetetraol, 2,3,5,7-octanetetraol, 4,5,6,7-octanetetraol, 3,7-dimethyl-3-octene-1,2,6,7-tetraol, 3-hexyn-1,2,5,6-tetraol, 2,5-dimethyl-3-hexyn-1,2,5,6-tetraol, anthracene-1,4,9,10-tetraol, or mixtures thereof.

[0066] The solvent may include one or more selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0067] Examples of the hydrocarbon solvents include, but are not limited to, aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane, and decane.

[0068] Examples of the ketone solvents include, but are not limited to, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate.

[0069] Examples of the ester-based solvents include, but are not limited to, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, and propyl lactate.

[0070] Examples of the alcohol-based solvents include, but are not limited to, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, ethylene glycol, diethylene glycol, and triethylene glycol.

[0071] Examples of the amide solvents include, but are not limited to, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone.

[0072] Examples of the ether-based solvents include, but are not limited to, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol, dioxane, and tetrahydrofuran.

[0073] If the rinsing solution of the present invention contains a solvent, the solvent may be present in an amount of 0.001% to 2% by weight of the total weight of the rinsing solution, preferably 0.01% to 1% by weight. The rinsing solution not containing a solvent is also one embodiment of the rinsing solution according to the present invention.

[0074] The water contained in the rinse solution of the present invention may be ultrapure water. The water in the rinse solution may be included as a residue, and the residue means the amount of residue that makes the total weight of the rinse solution, which further contains the essential components and other components, 100% by weight.

[0075] Specifically, if the rinse solution does not contain a solvent, water may be present in an amount of 98% to 99.9998% by weight of the total weight of the rinse solution, preferably 99% to 99.998% by weight. If the rinse solution contains a solvent, water may be present in an amount of 96% to 99.9988% by weight of the total weight of the rinse solution, preferably 97% to 99.988% by weight.

[0076] In one embodiment of the present invention, step (d) may further include a drying step. More specifically, step (d) may further include a spin-drying step to remove any remaining ultrapure water and rinse solution on the substrate after the ultrapure water washing step and the rinse solution washing step.

[0077] The drying steps may include a primary drying step in which the substrate is rotated at a speed of 1 rpm to 300 rpm for 1 second to 180 seconds, and a secondary drying step in which the substrate is rotated at a speed of 10 rpm to 3,000 rpm for 1 second to 120 seconds.

[0078] In one embodiment of the present invention, step (d) may be one in which isopropyl alcohol is not used.

[0079] The photoresist pattern formed by the photoresist pattern formation method of the present invention may have a line width (critical dimension, CD) of 25 nm or less, preferably 20 nm or less, and more preferably 18 nm or less.

[0080] Furthermore, the photoresist pattern formed by the photoresist pattern formation method of the present invention may have an aspect ratio (height / line width) of 1.5 or more, preferably 2.0 or more, and more preferably 2.2 or more.

[0081] The present invention will be described in more detail below through examples. However, the following examples are for illustrative purposes only, and the scope of the present invention is not limited to these examples.

[0082] <Examples> Examples 1-63 and Comparative Examples 1-9: Formation of Photoresist Patterns A chemically amplified PHS acrylate hydrate hybrid EUV resist was applied to a 12-inch silicon wafer (SK Siltron) using a spin coater and soft-baked at 110°C for 60 seconds to form a 400 Å thick photoresist film. The photoresist film on the wafer was exposed to an EUV lithography system through a mask to a size of 18 nm (line:space = 1:1) and post-exposure baking (PEB) was performed at 110°C for 60 seconds. The exposed photoresist film was paddle-developed for 32 seconds using a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH).

[0083] Ultrapure water was added to the developed photoresist film and the developer paddle on the wafer. The wafer was rotated at a speed of 1000 rpm, and ultrapure water was sprayed at a flow rate of 1500 ml / min for 60 seconds to replace the developer with ultrapure water. Then, the wafer was rotated at a speed of 500 rpm, and rinsing solution (0.001 wt% fluoroacrylic carboxylate, 0.001 wt% 1,2,3-propanetriol, and 99.998 wt% ultrapure water) was sprayed at a flow rate of 500 ml / min for 10 seconds to replace the ultrapure water with rinsing solution. After that, the wafer was rotated at a speed of 2000 rpm for 60 seconds to dry it.

[0084] The temperatures of the ultrapure water and rinsing solution used were as shown in Tables 1 and 2 below. Comparative Examples 1 to 8 did not undergo a rinsing solution washing step; the drying step was performed immediately after the ultrapure water washing step.

[0085] Furthermore, in the ultrapure water and rinse solution washing steps of Examples 1 to 63, the temperatures of the ultrapure water and rinse solution were kept constant at a preset temperature using the ultrapure water constant temperature device 100 and the rinse solution constant temperature device 200 shown in Figure 2.

[0086] On the other hand, in the ultrapure water and / or rinse solution washing step for Comparative Example 1 and Comparative Example 9, ultrapure water and / or rinse solution at room temperature (23°C) was used without using a separate constant temperature device.

[0087] [Table 1]

[0088] [Table 2] <Example of experiment> Evaluation of defects where the pattern collapses The patterns formed by the above examples and comparative examples were evaluated for pattern collapse defects using a critical dimension scanning microscope (CD-SEM, Hitachi). The number of collapse-free blocks among a total of 89 blocks on the wafer was confirmed, and the results are shown in Tables 3 and 4 below.

[0089] In connection with this, Figure 3 shows the results of evaluating defects in the pattern of the photoresist pattern formed by Example 47 of the present invention, and Figure 4 shows the results of evaluating defects in the pattern of the photoresist pattern formed by Comparative Example 1 of the present invention, with blocks where the pattern did not collapse being enclosed in a thick black solid line.

[0090] [Table 3]

[0091] [Table 4] Referring to Tables 3 and 4, it can be seen that Examples 1 to 63, which used ultrapure water and / or rinsing solution at 30°C to 90°C, showed superior results compared to Comparative Example 9, which used ultrapure water and rinsing solution at room temperature, with 65 or more blocks where the pattern did not collapse. In particular, in the example where both the ultrapure water and rinsing solution were sprayed at temperatures of 50°C to 80°C, it can be seen that even better results were observed, with 76 or more blocks where the pattern did not collapse.

[0092] On the other hand, Comparative Example 1, which used only room temperature ultrapure water in the washing stage after the developing stage, showed the lowest result with 33 blocks where the pattern did not collapse. Comparative Examples 2 to 8, which used only ultrapure water at 30°C to 90°C, had 48 or fewer blocks where the pattern did not collapse, indicating that even with high-temperature ultrapure water, defects such as pattern collapse cannot be prevented without a rinsing step.

Claims

1. (a) A step of applying a photoresist composition to a substrate to form a photoresist film; (b) Exposure step of irradiating the formed photoresist film with light; (c) developing the exposed photoresist film with a developer; and (d) A method for forming a photoresist pattern, comprising the step of washing the developed photoresist film, The (d) step includes, in order, an ultrapure water washing step and a rinse solution washing step, A method for forming a pattern, wherein at least one of the ultrapure water and rinsing solution in step (d) is sprayed at a temperature of 30°C to 90°C.

2. The method for forming a pattern according to claim 1, wherein at least one of the ultrapure water and rinsing solution in step (d) is sprayed at a temperature of 50°C to 80°C.

3. The method for forming a pattern according to claim 1, wherein at least one of the ultrapure water and rinsing solution in step (d) is sprayed at a temperature of 65°C to 75°C.

4. The method for forming a pattern according to claim 1, wherein the ultrapure water washing step involves spraying ultrapure water onto a substrate rotating at a speed of 1 rpm to 2,000 rpm at a flow rate of 1 ml / min to 2,000 ml / min for 1 second to 300 seconds.

5. The method for forming a pattern according to claim 1, wherein the rinse liquid washing step involves spraying rinse liquid onto a substrate rotating at a speed of 1 rpm to 1,500 rpm at a flow rate of 1 ml / min to 1,000 ml / min for 1 second to 100 seconds.

6. The method for forming a pattern according to claim 1, wherein the rinse solution comprises a surfactant, an additive, and water.

7. The rinse solution is, in relation to the total weight of the rinse solution, Surfactant 0.0001% to 1% by weight; Additives 0.0001% to 1% by weight; and A method for forming a pattern according to claim 6, including the remaining amount of water.

8. The method for forming a pattern according to claim 1, wherein the photoresist pattern has a line width of 25 nm or less.

9. The method for forming a pattern according to claim 1, wherein the photoresist pattern has an aspect ratio (height / line width) of 1.5 or more.

10. The method for forming a pattern according to claim 1, wherein the exposure source in step (b) is one selected from the group consisting of KrF, ArF, VUV, ArFi, and EUV.

11. A semiconductor device manufactured using the method for forming a photoresist pattern according to any one of claims 1 to 10.

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