METAL-CONTAINING PHOTORESIST DEVELOPMENT COMPOSITION AND METHOD FOR FORMING PATTERN INCLUDE DEVELOPMENT STEP USING THE SAME

Abstract

To provide a metal-containing photoresist developer composition that includes an organic solvent and a sulfonimide-based compound, and a method of forming patterns including a developing step using the composition.SOLUTION: A metal-containing photoresist developer composition includes an organic solvent, and a sulfonimide-based compound.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a metal-containing photoresist developer composition and a patterning method that includes a development step using the same. [Background technology]

[0002] Recently, the semiconductor industry has been accompanied by a continuing shrinkage of critical dimensions which has required a new class of high performance photoresist materials and patterning methods to meet the demands of fabricating and patterning smaller and smaller features.

[0003] Traditional chemically amplified (CA) photoresists were designed for high sensitivity, but may be more challenging under EUV exposure in part because their typical elemental makeup (mainly C with smaller quantities of O, F, S) reduces the absorbance of the photoresist at 13.5 nm wavelength, thereby reducing sensitivity. CA photoresists may also be challenged by roughness issues at small feature sizes, and experiments have shown that LER increases due to reduced photospeed, in part due to the nature of the acid catalysis process. Due to the shortcomings and problems of CA photoresists, there is a demand for a new type of high performance photoresist in the semiconductor industry.

[0004] In particular, there is a need to develop photoresists that can guarantee excellent etching resistance and resolution during the photolithography process while at the same time improving sensitivity and CD (critical dimension) uniformity and improving LER (line edge roughness) characteristics. Summary of the Invention [Problem to be solved by the invention]

[0005] In one embodiment, a metal-containing photoresist developer composition is provided. In another embodiment, a patterning method is provided that includes a development step using the composition. [Means for solving the problem]

[0006] A metal-containing photoresist developer composition according to one embodiment includes an organic solvent and a sulfonimide-based compound.

[0007] The sulfonimide compound may be at least one of compounds represented by the following Formula 1 and Formula 2.

[0008] [ka]

[0009] In the above Chemical Formula 1 and Chemical Formula 2, R 1 and R 2 are each independently fluorine, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C3-C20 cycloalkenyl group, a substituted or unsubstituted C3-C20 cycloalkynyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C1-C20 heteroaryl group, or a combination thereof; L 1 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C1 to C20 heteroarylene group, or a combination thereof.

[0010] The sulfonimide-based compound may be at least one of the compounds listed in Group I below.

[0011] [ka]

[0012] The sulfonimide compound may have a pKa of 5 or less.

[0013] The metal-containing photoresist developer composition according to one embodiment may contain 50 to 99.99% by weight of the organic solvent; and 0.01 to 50% by weight of the sulfonimide compound.

[0014] The metal compound contained in the metal-containing photoresist may be at least one of an organic oxy group-containing tin compound and an organic carbonyloxy group-containing tin compound.

[0015] The metal-containing photoresist may include a metal compound represented by the following Formula 3 or a condensate thereof.

[0016] [ka]

[0017] In the above Chemical Formula 3, R 3 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 arylalkyl group, and -L a -OR a (Here, L a is a substituted or unsubstituted C1-C20 alkylene group, R a is a substituted or unsubstituted C1 to C20 alkyl group; R 4 ~R 6each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, -OR b and -OC(=O)R c and R 4 ~R 6 At least one of the is -OR b and -OC(=O)R c is selected from among R b is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R c is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.

[0018] According to another embodiment, a method of forming a pattern includes the steps of applying a metal-containing photoresist composition on a substrate, applying a composition for removing edge bead of a metal-containing photoresist along an edge of the substrate, heat treating the substrate by drying and heating to form a metal-containing photoresist film on the substrate, exposing the metal-containing photoresist film to light, and applying and developing the metal-containing photoresist developer composition. Effect of the Invention

[0019] According to an embodiment of the present invention, a method for forming a pattern can minimize residual film, scum, and defects remaining in a metal-containing photoresist film after an exposure process and can facilitate development, thereby achieving excellent contrast characteristics. [Brief description of the drawings]

[0020] [Figure 1] 1A to 1C are cross-sectional views illustrating a process sequence for explaining a pattern forming method. [Diagram 2] 1A to 1C are cross-sectional views illustrating a process sequence for explaining a pattern forming method. [Diagram 3] 1A to 1C are cross-sectional views illustrating a process sequence for explaining a pattern forming method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in the following description, the description of the known functions or configurations will be omitted in order to clarify the gist of the description.

[0022] In order to clearly explain the present description, parts unnecessary for the description are omitted, and the same or similar components are designated by the same reference numerals throughout the specification. Furthermore, the size and thickness of each component shown in the drawings are arbitrarily shown for the convenience of explanation, and the present description is not necessarily limited to those shown in the drawings.

[0023] In the drawings, the thickness of a plurality of layers and regions is exaggerated to clearly show the layers and regions. Also, in the drawings, the thickness of some layers and regions is exaggerated for the convenience of explanation. When a layer, film, region, plate, or other part is said to be "on" another part, this includes not only the case where it is "directly on" the other part, but also the case where there is another part therebetween.

[0024] In this description, "substituted" means that the hydrogen atom is replaced with deuterium, a halogen group, a hydroxy group, an amino group, a substituted or unsubstituted C1-C30 amine group, a nitro group, a substituted or unsubstituted C1-C40 silyl group, a C1-C30 alkyl group, a C1-C10 haloalkyl group, a C1-C10 alkylsilyl group, a C3-C30 cycloalkyl group, a C6-C30 aryl group, a C1-C20 alkoxy group, or a cyano group. "Unsubstituted" means that the hydrogen atom remains as a hydrogen atom without being replaced with another substituent.

[0025] In this description, unless otherwise specified, the term "alkyl group" refers to a straight or branched chain aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0026] The alkyl group may be a C1-C20 alkyl group. More specifically, the alkyl group may be a C1-C10 alkyl group or a C1-C6 alkyl group. For example, a C1-C5 alkyl group means an alkyl group containing 1-5 carbon atoms in the alkyl chain, and is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and t-butyl.

[0027] Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0028] In this description, unless otherwise defined, a "cycloalkyl group" refers to a monovalent cyclic aliphatic hydrocarbon group.

[0029] In this description, unless otherwise defined, an "alkenyl group" refers to an aliphatic unsaturated alkenyl group which is a straight-chain or branched-chain aliphatic hydrocarbon group and contains one or more double bonds.

[0030] In this description, unless otherwise defined, an "alkynyl group" refers to an aliphatic unsaturated alkynyl group which is a straight-chain or branched-chain aliphatic hydrocarbon group and contains one or more triple bonds.

[0031] As used herein, the term "aryl group" refers to a substituent in which all elements of the cyclic group have p-orbitals and these p-orbitals form conjugation, including monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) functional groups.

[0032] Hereinafter, a metal-containing photoresist developer composition according to one embodiment will be described.

[0033] A metal-containing photoresist developer composition according to one embodiment of the present invention includes an organic solvent and a sulfonimide-based compound.

[0034] The metal-containing photoresist developer composition includes a sulfonimide-based compound, and the imide group of the sulfonimide-based compound is chelated to a resist containing a metal. Therefore, by applying a composition including the same, it is expected that a residual film / scum / defect that exists in a metal-containing photoresist film after an exposure process can be minimized and development can be easily performed, thereby achieving excellent contrast characteristics.

[0035] Since developers commonly used for metal-containing photoresist films mainly contain carboxylic acids, which are weak acids, they do not have sufficient cleaning power for metal-containing photoresist films, making it difficult to fully meet the requirements for processing and patterning smaller features due to pattern miniaturization.

[0036] On the other hand, the metal-containing photoresist developer composition according to an embodiment of the present invention uses a relatively strong acidic material including a sulfonimide-based compound compared to general carboxylic acids, and therefore has improved cleaning power and can sufficiently dissolve non-exposed areas, thereby minimizing residual film, scum, and defects and significantly reducing the pattern defect rate.

[0037] For example, the pKa of the sulfonimide compound may be −20≦pKa≦5, or more specifically, −15≦pKa≦5.

[0038] When the pKa of the sulfonimide-based compound is within the above range, the membrane removal ability can be further improved.

[0039] The sulfonimide compound may be at least one of compounds represented by the following Formula 1 and Formula 2.

[0040] [ka]

[0041] In the above Chemical Formula 1 and Chemical Formula 2, R 1 and R 2are each independently fluorine, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C3-C20 cycloalkenyl group, a substituted or unsubstituted C3-C20 cycloalkynyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C1-C20 heteroaryl group, or a combination thereof; L 1 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C1 to C20 heteroarylene group, or a combination thereof.

[0042] As an example, 1 and R 2 are each independently a fluorine, a C1-C20 alkyl group substituted or unsubstituted with at least one fluorine, a C2-C20 alkenyl group substituted or unsubstituted with at least one fluorine, a C2-C20 alkynyl group substituted or unsubstituted with at least one fluorine, a C3-C20 cycloalkyl group substituted or unsubstituted with at least one fluorine, a C3-C20 cycloalkenyl group substituted or unsubstituted with at least one fluorine, a C3-C20 cycloalkynyl group substituted or unsubstituted with at least one fluorine, a C6-C20 aryl group substituted or unsubstituted with at least one fluorine, a C1-C20 heteroaryl group substituted or unsubstituted with at least one fluorine, or a combination thereof; L 1 may be a C1 to C10 alkylene group substituted or unsubstituted with at least one fluorine, a C3 to C20 cycloalkylene group substituted or unsubstituted with at least one fluorine, a C6 to C20 arylene group substituted or unsubstituted with at least one fluorine, a C1 to C20 heteroarylene group substituted or unsubstituted with at least one fluorine, or a combination thereof.

[0043] As a specific example, 1 and R 2 each independently represents a fluorine, a C1-C20 alkyl group which is substituted or unsubstituted with at least one fluorine, a C3-C20 cycloalkyl group which is substituted or unsubstituted with at least one fluorine, a C6-C20 aryl group which is substituted or unsubstituted with at least one fluorine, or a combination thereof; L 1 may be a C1 to C5 alkylene group substituted or unsubstituted with at least one fluorine, a C3 to C10 cycloalkylene group substituted or unsubstituted with at least one fluorine, a C6 to C20 arylene group substituted or unsubstituted with at least one fluorine, or a combination thereof.

[0044] In one embodiment, the R 1 and R 2 each independently represents a fluorine atom, a C1-C10 alkyl group which is unsubstituted or substituted with at least one fluorine atom, a C6-C20 aryl group which is unsubstituted or substituted with at least one fluorine atom, or a combination thereof; L 1 can be a C1-C3 alkylene group unsubstituted or substituted with at least one fluorine.

[0045] For example, the sulfonimide compound may be at least one of the compounds listed in Group I below.

[0046] [ka]

[0047] In one embodiment, the metal-containing photoresist developer composition may contain 50 wt % to 99.99 wt % of an organic solvent and 0.01 wt % to 50 wt % of the sulfonimide-based compound.

[0048] Within this range, the sulfonimide compound may be contained in an amount of 40% by weight or less, specifically, 30% by weight or less, 20% by weight or less, or 10% by weight or less.

[0049] In a specific embodiment, the metal-containing photoresist developer composition may contain 0.01 to 40 wt %, specifically 0.01 to 30 wt %, more specifically 0.01 to 20 wt %, for example, 0.01 to 10 wt %.

[0050] Examples of organic solvents contained in the developer composition may include, but are not limited to, at least one of ethers, alcohols, glycol ethers, aromatic hydrocarbon compounds, ketones, and esters.For example, the organic solvent may be ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol, propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether, propylene glycol butyl ether acetate, ethanol, propanol, isopropyl alcohol, isobutyl alcohol, 4-methyl-2-pentanol (or methyl isobutyl carbinol (MIBC), hexanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol, propylene glycol, heptanone, propylene carbonate, butylene carbonate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, gamma-butyrolactone, methyl 2-hydroxyisobutyrate 2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate, or combinations thereof.

[0051] Developer compositions according to the present invention can be particularly effective in removing metal-containing resists, and more specifically, undesirable metal residues, such as tin-based metal residues.

[0052] In the case where the additives described below are included, the organic solvent may be included in an amount remaining excluding the components included therein.

[0053] The developer composition may further include at least one additive selected from the group consisting of a surfactant, a dispersant, a moisture absorbing agent, and a coupling agent.

[0054] The metal-containing resist composition can include a tin-based compound, for example the tin-based compound can be at least one of an organic oxy group-containing tin compound and an organic carbonyloxy group-containing tin compound.

[0055] For example, the metal compound or its condensate contained in the metal-containing resist may be represented by the following Chemical Formula 3.

[0056] [ka]

[0057] In the above Chemical Formula 3, R 3 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 arylalkyl group, and -L a -OR a (Here, L a is a substituted or unsubstituted C1-C20 alkylene group, R a is a substituted or unsubstituted C1 to C20 alkyl group; R 4 ~R 6each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, -OR b and -OC(=O)R c and R 4 ~R 6 At least one of the is -OR b and -OC(=O)R c is selected from among R b is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R c is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.

[0058] As an example, b and R c may each independently be a substituted or unsubstituted C1 to C20 alkyl group.

[0059] Meanwhile, according to another embodiment, a method for forming a pattern may be provided, comprising the step of developing using the above-mentioned metal-containing photoresist developer composition. For example, the pattern formed may be a negative type photoresist pattern.

[0060] Hereinafter, a pattern forming method according to an embodiment will be specifically described with reference to the drawings.

[0061] According to one embodiment, a method for forming a pattern includes the steps of: applying a metal-containing resist composition on a substrate; applying an edge bead removal composition along an edge of the substrate; heat treating the substrate by drying and heating to form a metal-containing resist film on the substrate; exposing the metal-containing resist film to light; and applying and developing a developer composition.

[0062] More specifically, the step of forming a pattern using the metal-containing resist composition may include a step of applying the metal-containing resist composition onto a substrate on which a thin film has been formed by spin coating, slit coating, inkjet printing, or the like, and a step of drying the applied metal-containing resist composition to form a resist film.

[0063] The metal-containing resist composition can include a tin-based compound. For example, the tin-based compound can include at least one of an organic oxy group-containing tin compound and an organic carbonyloxy group-containing tin compound.

[0064] A step of applying a composition for removing the edge bead of a metal-containing photoresist along the edge of the substrate may then be performed.

[0065] Specifically, the method may include applying an appropriate amount of the composition for removing edge bead of a metal-containing resist along the edge of a substrate, and then spinning the substrate at an appropriate speed (e.g., 1,000 rpm or more) after the composition for removing edge bead of a metal-containing resist is transferred to the substrate, thereby removing the bead on the substrate edge.

[0066] Next, a first heat treatment step is performed to heat the substrate on which the metal-containing resist film is formed. The first heat treatment step can be performed at a temperature of about 80° C. to about 120° C. During this process, the solvent is evaporated and the metal-containing resist film can be more firmly attached to the substrate.

[0067] The resist film is then selectively exposed to light using a patterned mask.

[0068] As an example, examples of light that can be used in the exposure process include light having wavelengths such as activation radiation i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), as well as light having high energy wavelengths such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).

[0069] More specifically, the exposure light according to an embodiment may be short-wavelength light having a wavelength range of 5 nm to 150 nm, and may be light having a high-energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0070] In the forming of the photoresist pattern, a negative type pattern may be formed.

[0071] The exposed area of ​​the photoresist film forms a polymer through a crosslinking reaction, such as condensation between organometallic compounds, and thus has a different solubility from the unexposed area of ​​the photoresist film.

[0072] Next, a second heat treatment step is performed on the substrate. The second heat treatment step can be performed at a temperature of about 90° C. to about 200° C. By performing the second heat treatment step, the exposed area of ​​the photoresist film becomes difficult to dissolve in a developer.

[0073] Specifically, the photoresist film corresponding to the unexposed area is dissolved and then removed using the above-mentioned photoresist developer, thereby completing the photoresist pattern corresponding to the negative tone image.

[0074] As described above, the photoresist pattern formed by exposure to light having a wavelength such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), as well as high-energy light such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam) may have a thickness width of 5 nm to 100 nm. As an example, the photoresist pattern may be formed with a thickness width of 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, or 5 nm to 20 nm.

[0075] Meanwhile, the photoresist pattern may have a half-pitch of about 50 nm or less, e.g., 40 nm or less, e.g., 30 nm or less, e.g., 20 nm or less, e.g., 15 nm or less, and a line width roughness of about 10 nm or less, about 5 nm or less, about 3 nm or less, about 2 nm or less.

[0076] Next, a method for forming a pattern will be specifically described with reference to the drawings.

[0077] 1 to 3 are cross-sectional views showing a process sequence for explaining a pattern forming method. Referring to Fig. 1, an exposed photoresist film is developed to form a photoresist pattern 130P.

[0078] In an exemplary embodiment, the exposed photoresist film may be developed to remove the unexposed areas of the photoresist film to form a photoresist pattern 130P consisting of the exposed areas of the photoresist film. The photoresist pattern 130P may include a plurality of openings OP.

[0079] In an exemplary embodiment, the development of the photoresist film may be performed by a negative-tone development (NTD) process, in which a metal-containing photoresist developer composition according to an embodiment may be used as a developer composition.

[0080] Referring to FIG. 2, the feature layer 110 is processed using the photoresist pattern 130P from the result of FIG.

[0081] For example, in order to process the feature layer 110, various processes may be performed, such as a process of etching the feature layer 110 exposed through the openings OP of the photoresist pattern 130P, a process of implanting impurity ions into the feature layer 110, a process of forming an additional film on the feature layer 110 through the openings OP, a process of deforming a part of the feature layer 110 through the openings OP, etc. FIG 2 illustrates an example process of processing the feature layer 110, in which the feature layer 110 exposed through the openings OP is etched to form a feature pattern 110P.

[0082] 3, the photoresist pattern 130P remaining on the feature pattern 110P is removed from the resultant structure of FIG 2. An ashing and stripping process can be used to remove the photoresist pattern 130P.

[0083] The present invention will be described in more detail below with reference to examples of the preparation of the above-mentioned metal-containing photoresist developer composition, but the technical features of the present invention are not limited to the following examples. EXAMPLES

[0084] Preparation of metal-containing photoresist developer compositions The organic solvent and the sulfonimide compound are mixed in a PP bottle according to the composition in Table 1 below, and then the mixture is completely dissolved by shaking at room temperature (25°C).Then, the mixture is passed through a PTFE filter having a pore size of 1 μm to obtain a developer composition.

[0085] [Table 1]

[0086] PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate MIBC: Methyl isobutyl carbinol EL: Ethyl lactate GBL: gamma-butyrolactone

[0087] Preparation of Metal-Containing Photoresist Compositions An organometallic compound having a structural unit represented by the following chemical formula C is dissolved in 4-methyl-2-pentanol to a concentration of 1 wt %, and then filtered through a 0.1 μm PTFE syringe filter to prepare a metal-containing photoresist composition.

[0088] [ka]

[0089] Evaluation 1: Evaluation of remaining film thickness 1.0 mL of the organometallic compound-containing photoresist composition according to the above Preparation Example was placed on a 4-inch silicon wafer, left for 20 seconds, and then spin-coated at a speed of 800 rpm for 30 seconds. Then, the wafer was treated at 100°C for 60 seconds, and then heat-treated again at 180°C for 60 seconds. 10 mL of each of the developer compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 4 was placed and spin-coated for 60 seconds, then dried by rotating at a speed of 1,500 rpm, and then heat-treated at 200°C for 60 seconds. The thickness of the resulting film was measured by ellipsometry to confirm the remaining film thickness after the development process, and the results were evaluated according to the following criteria, and are shown in Table 2 below. [Evaluation criteria for residual film thickness] *If the remaining film thickness is less than 1.0 nm: *Residual film thickness: 1.0nm or more and less than 3nm: △ *If the remaining film thickness is 3nm or more: X

[0090] Rating 2: Defect rating The prepared organometallic photoresist (PR) composition was spin-coated on an 8-inch wafer at 1,500 rpm for 30 seconds, and then heat-treated at 100° C. for 60 seconds to prepare a coated wafer. This was exposed to light with 20-100 mJ using a KrF scanner (ASML's PAS 5500 / 700D) with a 180 nm 1:1 line and space pattern, and then heat-treated at 180°C for 60 seconds. The developer compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 4 were applied to the resist pattern, and a development process was carried out at 1500 rpm for 30 seconds, followed by curing at 240°C for 60 seconds.

[0091] After the curing process was completed, the patterned wafer with the line / space CD pattern formed thereon was transferred to a CD-SEM measurement device to obtain a CD-SEM image. Among the CD-SEM images, an image having a space CD of 180 nm was selected, and the defect (scum, bridge, pattern collapse) area ratio in the space portion was evaluated using the Macview (Mountech) program according to the following criteria, and the results are shown in Table 2 below. [Defect evaluation criteria] -A: No defects -B: Defects less than 10% -C: Defects 10% or more

[0092] [Table 2]

[0093] Referring to Table 2, it can be seen that the metal-containing photoresist developer compositions according to Examples 1 to 12 have excellent metal-containing photoresist film removal capabilities compared to the metal-containing photoresist developer compositions according to Comparative Examples 1 to 4, and thus excellent pattern characteristics with minimized defects can be achieved.

[0094] Although specific embodiments of the present invention have been described and illustrated above, it is obvious to those skilled in the art that the present invention is not limited to the described embodiments, and that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modifications or variations should not be understood individually from the technical spirit and perspective of the present invention, and the modified embodiments should be considered to belong to the scope of the claims of the present invention. [Explanation of symbols]

[0095] 100...substrate, OP...opening, 110...feature layer, 110P...feature pattern, 130P...photoresist pattern.

Claims

1. an organic solvent, and A metal-containing photoresist developer composition comprising a sulfonimide-based compound.

2. 2. The metal-containing photoresist developer composition according to claim 1, wherein the sulfonimide compound is at least one of compounds represented by the following Formula 1 and Formula 2: 【Chemistry 1】 (In the above Chemical Formula 1 and Chemical Formula 2, R １ and R ２ are each independently fluorine, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C3-C20 cycloalkenyl group, a substituted or unsubstituted C3-C20 cycloalkynyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C1-C20 heteroaryl group, or a combination thereof; L １ is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C1 to C20 heteroarylene group, or a combination thereof.

3. 2. The metal-containing photoresist developer composition according to claim 1, wherein the sulfonimide compound is at least one of the compounds listed in Group I below. 【Chemistry 2】

4. 2. The metal-containing photoresist developer composition according to claim 1, wherein the sulfonimide compound has a pKa of 5 or less.

5. 50 to 99.99% by weight of said organic solvent; and 2. The metal-containing photoresist developer composition according to claim 1, comprising 0.01 to 50% by weight of said sulfonimide compound.

6. 2. The metal-containing photoresist developer composition according to claim 1, wherein the metal compound contained in the metal-containing photoresist is at least one of an organic oxy group-containing tin compound and an organic carbonyloxy group-containing tin compound.

7. 2. The metal-containing photoresist developer composition of claim 1, wherein the metal-containing photoresist comprises a metal compound represented by the following Formula 3 or a condensate thereof: 【Chemistry 3】 (In the above Chemical Formula 3, R ３ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 arylalkyl group, and -L ａ -O-R ａ (Here, L ａ is a substituted or unsubstituted C1 to C20 alkylene group, R ａ is a substituted or unsubstituted C1 to C20 alkyl group; R ４ ~R ６ each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, -OR ｂ and -OC(=O)R ｃ and R ４ ~R ６ At least one of the groups is -OR ｂ and -OC(=O)R ｃ is selected from among R ｂ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof; R ｃ is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.

8. applying a metal-containing photoresist composition onto a substrate; applying a composition for removing edge bead of metal-containing photoresist to the substrate; a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate; exposing the metal-containing photoresist film to light; and A step of applying and developing a metal-containing photoresist developer composition according to any one of claims 1 to 7, Pattern formation method.

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