Developer composition for a metal-containing photoresist, and a patterning method including a developing step using the same

Abstract

To provide a metal-containing photoresist developer composition, and a method of forming patterns including a developing step utilizing the metal-containing photoresist developer composition.SOLUTION: A metal-containing photoresist developer composition includes an organic solvent, an acid compound with a first acid dissociation constant pKa1 of 1.0≤pKa1≤4.8, and at least one alcohol-based compound, which is at least one of a diol compound derived from an acyclic hydrocarbon and a cyclic alcohol compound.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a developer composition for a metal-containing photoresist and a patterning method including a developing process using the same.

Background Art

[0002] Recently, in the semiconductor industry, there has been a continuous reduction in critical dimensions. Due to such dimensional reduction, new types of high-performance photoresist materials and patterning methods are required to satisfy the requirements for processing and patterning of ever-smaller features.

[0003] Conventional chemically amplified (CA) photoresists are designed for high sensitivity, but their typical elemental compositions (mainly C (carbon) having smaller quantities of O (oxygen), F (fluorine), S (sulfur)) reduce the absorbance of the photoresist at a wavelength of 13.5 nm. As a result, due to the decrease in sensitivity, it may be more problematic, in part, under EUV exposure. CA photoresists may also be troubled by roughness issues at small feature sizes, and it has been experimentally shown that LER (line edge roughness) increases due to a decrease in photospeed, in part due to the nature of the acid-catalyzed process. Due to the drawbacks and problems of CA photoresists, there is a need in the semiconductor industry for new types of high-performance photoresists.

[0004] In particular, there is a need to develop a photoresist that can maintain excellent etching resistance and resolution in the photolithography process, while improving sensitivity and the uniformity of critical dimensions, and can improve LER (line edge roughness) characteristics.

Prior Art Documents

Patent Documents

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-195517 [Patent Document 2] Japanese Patent No. 3417432 [Summary of the Invention] [Problems to be Solved by the Invention]

[0006] An object of the present invention is to provide a developer composition for a metal-containing photoresist that can achieve excellent contrast characteristics, excellent sensitivity, and reduction of line edge roughness.

[0007] Another object of the present invention is to provide a patterning method including a developing step using the above developer composition for a metal-containing photoresist. [Means for Solving the Problems]

[0008] A developer composition for a metal-containing photoresist according to an embodiment of the present invention includes an organic solvent, an acid compound having a first acid dissociation constant pKa1 in the range of 1.0 ≦ pKa1 ≦ 4.8, and at least one alcohol compound selected from a diol compound and a cyclic alcohol compound derived from an acyclic hydrocarbon.

[0009] The pKa1 of the acid compound may be 1.0 ≦ pKa1 ≦ 4.5.

[0010] The above acid compound may be at least one selected from the group consisting of phosphoric acid, phosphonic acid, methylphosphonic acid, ethylphosphonic acid, butylphosphonic acid, hexylphosphonic acid, n-octylphosphonic acid, tetradecylphosphonic acid, octadecylphosphonic acid, phenylphosphonic acid, vinylphosphonic acid, 6-hydroxyhexylphosphonic acid, decylphosphonic acid, methylenediphosphonic acid, nitrilotrimethylenetriphosphonic acid, diphenylphosphinic acid, bis(4-methoxyphenyl)phosphinic acid, phosphinic acid, bis(hydroxymethyl)phosphinic acid, phenylphosphinic acid, P-(3-aminopropyl)-P-butylphosphinic acid, chloroacetic acid, formic acid, and acetic acid.

[0011] The diol compound derived from the above acyclic hydrocarbon may be a compound represented by the following Chemical Formula 1 or Chemical Formula 2.

[0012]

Chemical Formula

[0013] In the above Chemical Formula 1 and Chemical Formula 2, R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, n and m are each independently an integer of 2 or more.

[0014] The above cyclic alcohol compound may be a compound represented by the following Chemical Formula 3 or Chemical Formula 4.

[0015]

Chemical Formula

[0016] In the above Chemical Formula 3 and Chemical Formula 4, R 3 ~R 13are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a nitro group, a substituted or unsubstituted amino group having 1 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, At this time, R 8 ~R 13 at least one of which is a hydroxy group.

[0017] The above-described developer composition for a metal-containing photoresist can contain, based on the total mass of the developer composition for a metal-containing photoresist, 0.05 to 10% by mass of the total mass of the above acid compound and the above alcohol-based compound, and the remaining amount of the above organic solvent.

[0018] The above acid compound and the above alcohol-based compound may be contained in a mass ratio of 1:0.5 to 1:200.

[0019] The above metal-containing photoresist can contain a metal compound containing at least one of an organotin iodine group, an organotin organic oxy group, an organotin carboxy group, and an organotin hydroxy group.

[0020] The above metal compound can be a compound represented by the following Chemical Formula 5 or a condensate thereof.

[0021]

Chemical Formula

[0022] In the above Chemical Formula 5, R 14 is 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 -R a -O-R b (wherein, R ais an alkylene group having 1 to 20 carbon atoms, which may be substituted or unsubstituted, and R b is an alkyl group having 1 to 20 carbon atoms, which may be substituted or unsubstituted), and R 15 ~R 17 are each independently an alkyl group having 1 to 20 carbon atoms, which may be substituted or unsubstituted, a cycloalkyl group having 3 to 20 carbon atoms, which may be substituted or unsubstituted, an alkenyl group having 2 to 20 carbon atoms, which may be substituted or unsubstituted, an alkynyl group having 2 to 20 carbon atoms, which may be substituted or unsubstituted, an aryl group having 6 to 30 carbon atoms, which may be substituted or unsubstituted, an arylalkyl group having 6 to 30 carbon atoms, which may be substituted or unsubstituted, -OR c , and -OC(=O)R d selected from among, and R 15 ~R 17 at least one of which is selected from -OR c and -OC(=O)R d selected from among, R c is an alkyl group having 1 to 20 carbon atoms, which may be substituted or unsubstituted, a cycloalkyl group having 3 to 20 carbon atoms, which may be substituted or unsubstituted, an alkenyl group having 2 to 20 carbon atoms, which may be substituted or unsubstituted, an alkynyl group having 2 to 20 carbon atoms, which may be substituted or unsubstituted, an aryl group having 6 to 30 carbon atoms, which may be substituted or unsubstituted, or a combination thereof, R d is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, which may be substituted or unsubstituted, a cycloalkyl group having 3 to 20 carbon atoms, which may be substituted or unsubstituted, an alkenyl group having 2 to 20 carbon atoms, which may be substituted or unsubstituted, an alkynyl group having 2 to 20 carbon atoms, which may be substituted or unsubstituted, an aryl group having 6 to 30 carbon atoms, which may be substituted or unsubstituted, or a combination thereof.

[0023] R c and R d may each independently be an alkyl group having 1 to 20 carbon atoms, which may be substituted or unsubstituted.

[0024] The pattern formation method according to another embodiment of the present invention includes a step of applying a metal-containing photoresist composition on a substrate, a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate, a step of exposing the metal-containing photoresist film, and a step of developing using the above-described developer composition for a metal-containing photoresist.

Advantages of the Invention

[0025] According to the present invention, a developer composition for a metal-containing photoresist capable of realizing excellent contrast characteristics, excellent sensitivity, and reduction of line edge roughness can be provided.

Brief Description of the Drawings

[0026]

Figure 1

Figure 2

Figure 3

Embodiments for Carrying Out the Invention

[0027] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings. However, in the description of the present invention, descriptions of already known functions or configurations will be omitted in order to clarify the gist of the present invention.

[0028] In order to clearly explain the present invention, parts that are unnecessary for explanation are omitted, and the same or similar components throughout the specification are given the same reference numerals. Also, the sizes and thicknesses of the respective configurations shown in the drawings are arbitrarily shown for the convenience of explanation, and the present invention is not necessarily limited to the places shown in the drawings.

[0029] For the purpose of clearly showing various layers and regions in the drawings, the thicknesses are shown enlarged. And for the convenience of explanation in the drawings, the thicknesses of some layers and regions are shown exaggerated. When a part such as a layer, film, region, plate, etc. is "on" or "above" another part, this includes not only the case where it is "directly above" the other part, but also the case where there are other parts in between.

[0030] As used herein, "substituted" means that a hydrogen atom is substituted with a deuterium atom, a halogen atom, a hydroxy group, an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a nitro group, a substituted or unsubstituted silyl group having 1 to 40 carbon atoms, an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a cyano group. "Unsubstituted" means that the hydrogen atom remains as a hydrogen atom without being substituted with other substituents.

[0031] As used herein, the term "alkyl group" means a linear, branched, or cyclic aliphatic hydrocarbon group, unless otherwise defined. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

[0032] The above alkyl group may be an alkyl group having 1 to 20 carbon atoms. More specifically, the alkyl group may be an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 6 carbon atoms. For example, an alkyl group having 1 to 4 carbon atoms means that the alkyl chain contains 1 to 4 carbon atoms, and means a group selected from the group consisting of, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

[0033] The above alkyl group, for example, specifically means a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc.

[0034] In this specification, unless otherwise defined, the "cycloalkyl group" means a monovalent alicyclic hydrocarbon group.

[0035] In this specification, unless otherwise defined, the "alkenyl group" means a linear or branched aliphatic hydrocarbon group containing one or more double bonds, i.e., an aliphatic unsaturated alkenyl group.

[0036] In this specification, unless otherwise defined, the "alkynyl group" means a linear or branched aliphatic hydrocarbon group containing one or more triple bonds, i.e., an aliphatic unsaturated alkynyl group.

[0037] In this specification, the "aryl group" means a substituent in which all elements of the cyclic substituent have p-orbitals and these p-orbitals form conjugation, and includes a monocyclic or condensed polycyclic (i.e., rings sharing adjacent pairs of carbon atoms) functional group.

[0038] Hereinafter, a developer composition for a metal-containing photoresist according to an embodiment of the present invention will be described.

[0039] A developer composition for a metal-containing photoresist according to an embodiment of the present invention contains an organic solvent, an acid compound having a first acid dissociation constant pKa1 in the range of 1.0 ≦ pKa1 ≦ 4.8, and an alcohol-based compound which is at least one of a diol compound and a cyclic alcohol compound derived from an acyclic hydrocarbon.

[0040] The pKa1 of the above acid compound may be in the range of 1.0 ≦ pKa1 ≦ 4.5.

[0041] The above acid compound may be at least one selected from the group consisting of phosphoric acid, phosphonic acid, methylphosphonic acid, ethylphosphonic acid, butylphosphonic acid, hexylphosphonic acid, n-octylphosphonic acid, tetradecylphosphonic acid, octadecylphosphonic acid, phenylphosphonic acid, vinylphosphonic acid, 6-hydroxyhexylphosphonic acid, decylphosphonic acid, methylenediphosphonic acid, nitrilotrimethylenetriphosphonic acid, diphenylphosphinic acid, bis(4-methoxyphenyl)phosphinic acid, phosphinic acid, bis(hydroxymethyl)phosphinic acid, phenylphosphinic acid, P-(3-aminopropyl)-P-butylphosphinic acid, chloroacetic acid, formic acid, and acetic acid.

[0042] As an example, the above acid compound may be at least one selected from the group consisting of phosphoric acid, phosphonic acid, methylphosphonic acid, butylphosphonic acid, phenylphosphonic acid, vinylphosphonic acid, chloroacetic acid, formic acid, and acetic acid.

[0043] The diol compound derived from the above acyclic hydrocarbon may be a diol compound derived from a saturated hydrocarbon or an unsaturated hydrocarbon, and may be, for example, a compound represented by the following Chemical Formula 1 or Chemical Formula 2.

[0044]

Chemical formula

[0045] In the above Chemical Formula 1 and Chemical Formula 2, R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, n and m are each independently an integer of 2 or more.

[0046] As an example, the diol compound derived from the above acyclic hydrocarbon may be at least one selected from the group consisting of 1,2-ethanediol, propylene glycol, 2-butene-2,3-diol, 2-hexene-2,3-diol, and 1,2-butanediol.

[0047] The above cyclic alcohol compound may be a compound represented by the following Chemical Formula 3 or Chemical Formula 4.

[0048]

Chemical formula

[0049] In the above Chemical Formula 3 and Chemical Formula 4, R 3 ~R 13 are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a nitro group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, At this time, at least one of 8 R 13 ~R

[0050] is a hydroxy group. 3 ~R 7 As an example, at least one of

[0051] R

[0052]

Chemical formula

[0053] In the above Group 1, R 3 ~R 13are each independently a hydrogen atom, a halogen atom, an amino group, a nitro group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

[0054] For example, the cyclic alcohol compound may be at least one selected from the group consisting of pyrocatechol compounds listed in Group 2 below and tropolone.

[0055] [Chemical formula]

[0056] The above developer composition for a metal-containing photoresist can contain, based on the total mass of the developer composition for a metal-containing photoresist, 0.05 to 10% by mass of the total mass of the acid compound and the alcohol-based compound, and the balance of the organic solvent.

[0057] The acid compound and the alcohol-based compound may be contained in a mass ratio of 1:0.5 to 1:200.

[0058] As an example, the acid compound and the alcohol-based compound may be contained in a mass ratio of 1:1 to 1:200, and for example, may be contained in a mass ratio of 1:1 to 1:100.

[0059] Within the above content range, the content of the acid compound may be less than 1% by mass, specifically may be 0.9% by mass or less, and more specifically may be 0.8% by mass or less.

[0060] Within the above content range, the content of the alcohol-based compound may be less than 10% by mass, specifically may be 9% by mass or less, more specifically may be 8% by mass or less, or 7% by mass or less, and for example, may be 5% by mass or less.

[0061] By applying a developer composition for a metal-containing photoresist containing this, defects present in the metal-containing photoresist film after the exposure step are minimized, and by making it easily developable, excellent pattern characteristics can be realized.

[0062] Moreover, according to the present invention, excellent sensitivity and reduced line edge roughness (LER) can also be realized.

[0063] On the other hand, by adding the acid compound according to the present invention, the line edge roughness and pattern formability can be improved. Although a decrease in pattern formability may occur depending on the molecular size of the acid compound, by adding the alcohol-based compound according to the present invention together, this can be complemented, so that a remarkably improved effect in pattern formability can be obtained.

[0064] In addition, in this specification, the first acid dissociation constant pKa1 is a value measured at 25°C. The values described in the catalog or technical materials of the acid compound may be adopted.

[0065] Examples of the organic solvent contained in the developer composition for a metal-containing photoresist according to an embodiment of the present invention include, but are not limited to, at least one selected from the group consisting 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 can be described as 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-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, γ-butyrolactone, methyl-2-hydroxyisobutyrate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate, or a combination thereof, but are not limited thereto.

[0066] When other additives are included, the above organic solvent may be included in the remaining amount excluding the components contained therein.

[0067] The metal-containing photoresist to be developed with the above developer composition for metal-containing photoresists can contain a metal compound containing at least one selected from the group consisting of an organotin iodine group, an organotin organic oxy group, an organotin carboxy group, and an organotin hydroxy group.

[0068] As an example, the above metal compound can be a compound represented by the following Chemical Formula 5 or a condensate thereof.

[0069] [Chemical Formula]

[0070] In the above Chemical Formula 5, R 14 is 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, and -R a -O-R b (wherein R a is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, and R b is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms), and is selected from among R 15 ~R 17 are each independently 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 6 to 30 carbon atoms, -OR c and -OC(=O)R dselected from among them and R 15 ~R 17 at least one of which is -OR c and -OC(=O)R d selected from among At this time, R c is 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, or a combination thereof, R d is a hydrogen atom, 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, or a combination thereof.

[0071] As an example, the metal compound can include at least one selected from the group consisting of an alkyltin iodine group, an alkyltin alkoxy group, an alkyltin carboxy group, and an alkyltin hydroxy group.

[0072] For example, the above R c and R d may each independently be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

[0073] In addition, the metal compound may be in the form of an oligomer or a polymer.

[0074] On the other hand, according to another embodiment of the present invention, a pattern forming method including a developing step using the above-described developer composition for a metal-containing photoresist can be provided. As an example, the produced pattern may be a negative photoresist pattern.

[0075] A pattern formation method according to an embodiment of the present invention includes a step of applying a metal-containing photoresist composition onto a substrate, a heat treatment step of drying and heating the applied metal-containing photoresist composition to form a metal-containing photoresist film on the substrate, a step of exposing the metal-containing photoresist film, and a step of developing using the above-described developer composition for metal-containing photoresist.

[0076] More specifically, the step of forming a pattern using a metal-containing photoresist composition may include a step of applying the metal-containing photoresist composition onto a substrate on which a thin film is formed by spin coating, slit coating, inkjet printing, etc., and a step of drying the applied metal-containing photoresist composition to form a photoresist film. The metal-containing photoresist composition may contain a tin-based compound. For example, the tin-based compound may contain at least one selected from the group consisting of an alkyltin iodine group, an alkyltin alkoxy group, an alkyltin carboxy group, and an alkyltin hydroxy group.

[0077] Next, a first heat treatment step of heating the substrate on which the metal-containing photoresist film is formed is performed. The first heat treatment step can be performed at a temperature of 80°C to 120°C. In this process, the solvent evaporates, and the metal-containing photoresist film can adhere more firmly to the substrate.

[0078] Then, the photoresist film is selectively exposed.

[0079] As an example, examples of light that can be used in the exposure step include not only light having a short wavelength such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), but also light having a high energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm), E-Beam (electron beam), etc.

[0080] More specifically, the light for exposure according to an embodiment of the present invention may be short-wavelength light having a wavelength range of 5 nm to 150 nm, and may also be light having a high-energy wavelength such as EUV (extreme ultraviolet; wavelength 13.5 nm) or E-Beam (electron beam).

[0081] In the step of forming the photoresist pattern, a negative pattern can be formed.

[0082] The exposed region in the photoresist film forms a polymer by a crosslinking reaction such as condensation between organometallic compounds, and thus has a solubility different from that of the unexposed region of the photoresist film.

[0083] Next, a second heat treatment step is performed on the substrate. The second heat treatment step can be performed at a temperature of 90°C to 200°C. By performing the second heat treatment step, the exposed region of the photoresist film becomes difficult to dissolve in the developer.

[0084] Specifically, by using the above-described developer composition for a metal-containing photoresist to dissolve and remove the photoresist film corresponding to the unexposed region, a photoresist pattern corresponding to a negative tone image can be completed.

[0085] As described above, not only light having wavelengths such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), but also light having high energy such as EUV (extreme ultraviolet; wavelength 13.5 nm) and E-Beam (electron beam) can form a photoresist pattern having a width of 5 nm to 100 nm. As an example, the photoresist pattern can be formed with widths 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, and 5 nm to 20 nm.

[0086] On the one hand, the photoresist pattern can have a half pitch of 50 nm or less, for example 40 nm or less, for example 30 nm or less, for example 20 nm or less, for example 15 nm or less, and a pitch with a line width roughness of 10 nm or less, 5 nm or less, 3 nm or less, 2 nm or less.

[0087] The method of forming a pattern will be specifically described below by taking the drawings as examples.

[0088] FIGS. 1 to 3 are schematic cross-sectional views shown in the order of steps to explain the pattern forming method.

[0089] Referring to FIG. 1, the exposed photoresist film is developed to form a photoresist pattern 130P.

[0090] In an exemplary embodiment, the exposed photoresist film can be developed to remove the unexposed regions of the photoresist film, and a photoresist pattern 130P composed of the exposed regions of the photoresist film can be formed. The photoresist pattern 130P can include a plurality of openings OP.

[0091] In an exemplary embodiment, the development of the photoresist film can be performed in an NTD (negative-tone development) process. At this time, the developer composition for a metal-containing photoresist according to an embodiment of the present invention can be used as the developer composition.

[0092] Referring to FIG. 2, the feature layer 110 is processed using the photoresist pattern 130P which is the result of FIG. 1.

[0093] For example, in order to process the feature layer 110, various processes can be performed, such as etching the feature layer 110 exposed through the opening OP of the photoresist pattern 130P, implanting impurity ions into the feature layer 110, forming an additional film on the feature layer 110 through the opening OP, and deforming a part of the feature layer 110 through the opening OP. FIG. 2 illustrates a case where the feature layer 110 exposed through the opening OP is etched to form a feature pattern 110P as an exemplary process for processing the feature layer 110.

[0094] Referring to FIG. 3, the photoresist pattern 130P remaining on the feature pattern 110P, which is the result of FIG. 2, is removed. To remove the photoresist pattern 130P, ashing and stripping processes can be used.

Example

[0095] Hereinafter, the present invention will be described in more detail through examples related to the production of the above-described developer composition for a metal-containing photoresist. However, the technical features of the present invention are not limited by the following examples.

[0096] (Production of Developer Composition for Metal-Containing Photoresist) An organic solvent and an additive were mixed in the composition shown in Table 1 below in a PP bottle, and then shaken at room temperature (25°C) to be completely dissolved. Thereafter, the composition was passed through a PTFE filter having a pore size of 1 μm to obtain a developer composition. The numerical values in parentheses in Table 1 below represent the content (unit: mass%) of each component.

[0097]

Table 1

[0098] (Production of Metal-Containing Photoresist Composition) An organometallic compound having a structural unit represented by the following chemical formula C was dissolved in 4-methyl-2-pentanol at a concentration of 1% by mass, and then filtered using a 0.1-μm PTFE syringe filter to produce a metal-containing photoresist composition.

[0099] [Chemical formula]

[0100] (Production of Metal-Containing Photoresist Pattern) The 8-inch silicon wafer was coated with the metal-containing photoresist composition produced above and soft-baked at 180°C for 60 seconds. The coated wafer was exposed with different exposure doses using a KrF scanner manufactured by Nikon Corporation. The exposed wafer was immersed in the developer according to Examples 1 to 9 and Comparative Examples 1 to 4 for 30 seconds each, and then additionally washed with the same developer for 15 seconds to form a negative-tone image, that is, the unexposed coating portion was removed. Finally, hot plate baking was performed at 240°C for 60 seconds to complete the process and produce a photoresist pattern.

[0101] (Evaluation 1: Measurement of Pattern Top-Bottom Difference) For the pattern produced above, using a field emission scanning electron microscope (FE-SEM), the sizes of the upper and lower parts of the 1:1 pattern line confirmed from the image were measured, and the value obtained by dividing the upper pattern size by the lower pattern size was defined as the "top-bottom difference". The numerical value of the top-bottom difference was expressed as a percentage and evaluated according to the following criteria.

[0102] [Top-Bottom Difference] ○: More than 70% ×: 70% or less.

[0103] Evaluation 2: Sensitivity and Line Edge Roughness (LER) Evaluation For the pattern manufactured above, the 1:1 pattern line size was measured using a length-measuring SEM (CD-SEM), and the energy at the target pattern size value was set as the sensitivity. At this time, after measuring the line edge roughness (LER) of the line at the said sensitivity, the line edge roughness was evaluated in two steps according to the following criteria and shown in Table 2 below.

[0104] [Sensitivity] ○: 120 mJ / cm 2 Below ×: 120 mJ / cm 2 Over [Line Edge Roughness (LER)] ○: 2.6 nm or less ×: Over 2.6 nm.

[0105]

Table 2

[0106] Referring to Table 2, when applying the developer composition for a metal-containing photoresist according to Examples 1 to 9, it can be confirmed that, compared with the case of applying the developer composition for a metal-containing photoresist according to Comparative Examples 1 to 4, excellent pattern characteristics, excellent sensitivity, and reduced line edge roughness are shown.

[0107] As described above, specific examples of the present invention have been described and illustrated. However, the present invention is not limited to the described examples, and it is obvious to those having ordinary knowledge in this technical field that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modified examples or variations should not be individually understood from the technical idea or perspective of the present invention, and the modified examples should be said to belong to the scope of the claims of the present invention.

Explanation of Signs

[0108] 100 Substrate, OP Opening, 110 Feature Layer, 110P Feature Pattern, 130P photoresist pattern.

Claims

1. An organic solvent, an acid compound having a first acid dissociation constant pKa1 in the range of 1.0 ≦ pKa1 ≦ 4.8, and an alcohol-based compound which is at least one of a diol compound derived from an acyclic hydrocarbon and a cyclic alcohol compound A developer composition for a metal-containing photoresist, comprising: The acid compound and the alcohol-based compound are contained in a mass ratio of 1:0.5 to 1:

200. A developer composition for a metal-containing photoresist.

2. The developer composition for a metal-containing photoresist according to claim 1, wherein the first acid dissociation constant pKa1 of the acid compound is in the range of 1.0 ≦ pKa1 ≦ 4.

5.

3. The acid compound is at least one selected from the group consisting of phosphoric acid, phosphonic acid, methylphosphonic acid, ethylphosphonic acid, butylphosphonic acid, hexylphosphonic acid, n-octylphosphonic acid, tetradecylphosphonic acid, octadecylphosphonic acid, phenylphosphonic acid, vinylphosphonic acid, 6-hydroxyhexylphosphonic acid, decylphosphonic acid, methylenediphosphonic acid, nitrilotrimethylenetriphosphonic acid, diphenylphosphinic acid, bis(4-methoxyphenyl)phosphinic acid, phosphinic acid, bis(hydroxymethyl)phosphinic acid, penylphosphinic acid, P-(3-aminopropyl)-P-butylphosphinic acid, chloroacetic acid, formic acid, and acetic acid. The developer composition for a metal-containing photoresist according to claim 1.

4. The diol compound derived from the acyclic hydrocarbon is a compound represented by the following Chemical Formula 1 or Chemical Formula 2. The developer composition for a metal-containing photoresist according to claim 1: 【Chemical Formula 1】 In the Chemical Formula 1 and Chemical Formula 2, R １ and R ２ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, n and m are each independently an integer of 2 or more.

5. The cyclic alcohol compound is a compound represented by the following Chemical Formula 3 or Chemical Formula 4. The developer composition for a metal-containing photoresist according to claim 1: [Chemical 2] In the Chemical Formula 3 and Chemical Formula 4, R ３ to R １３ each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a nitro group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, At this time, R ８ ~R １３ At least one of them is a hydroxy group.

6. The developer composition for a metal-containing photoresist is 0.05 to 10% by mass in total of the acid compound and the alcohol-based compound with respect to the total mass of the developer composition for a metal-containing photoresist, and the balance of the organic solvent. The developer composition for a metal-containing photoresist according to claim 1.

7. The developer composition for a metal-containing photoresist according to claim 6, wherein the acid compound is contained in an amount of less than 1% by mass, and the alcohol-based compound is contained in an amount of 9% by mass or less.

8. The developer composition for a metal-containing photoresist according to claim 1, wherein the metal-containing photoresist contains a metal compound containing at least one selected from the group consisting of an organotin iodine group, an organotin organic oxy group, an organotin carboxy group, and an organotin hydroxy group.

9. The developer composition for a metal-containing photoresist according to claim 8, wherein the metal compound is a compound represented by the following chemical formula 5 or a condensate thereof: [Chemical 3] In the chemical formula 5, R １４ is 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, and -R ａ -O-R ｂ (wherein R ａ is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, and R ｂ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms) is selected from among R １５ ~R １７ are each independently 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 6 to 30 carbon atoms, -OR ｃ , and -OC(=O)R ｄ selected from among, and R １５ ~R １７ at least one of is selected from among -OR ｃ and -OC(=O)R ｄ selected from among, At this time, R ｃ is 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, or a combination thereof, R ｄ is a hydrogen atom, 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, or a combination thereof.

10. A step of applying a metal-containing photoresist composition onto a substrate; A heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate; A step of exposing the metal-containing photoresist film; and A step of developing using the developer composition for a metal-containing photoresist according to any one of claims 1 to 9; A pattern forming method comprising the above steps.

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