Precursor compound, composition prepared therefrom, and method for forming thin film comprising same

Abstract

One embodiment of the present invention provides a precursor compound comprising non-metal elements bonded to three or more metals, specifically, comprising three to six metals and non-metal elements, wherein at least one of the non-metal elements is bonded to each of the three or more metals, at least one of the non-metal elements is connected to the same kind of metals, and the metals can be bonded to the non-metal elements and a functional group. A composition comprising: the compound; and a solvent, and a thin film may be formed by coating the composition.

Description

Precursor compound, composition prepared therefrom, and method for forming a thin film comprising the same

[0001] The present invention relates to a precursor compound, a composition prepared therefrom, and a method for forming a thin film comprising the same, and more particularly, to a method for forming a thin film capable of securing an EUV resist with excellent etching resistance, improved productivity, and reduced shot noise by providing a precursor compound and coating a composition prepared from the precursor compound.

[0002] Photoresist (PR) is a chemical substance whose properties change in response to light. In displays, it is used in the photolithography process, which forms fine circuits on thin-film transistors (TFTs).

[0003] Photoresist's chemical properties change when exposed to light. Depending on the type, it hardens or melts when exposed to light. Photolithography utilizes these changes in photoresist properties to selectively remove only the weakened portions, distinguishing between those that will be used as circuits and those that will not, and creates a fine, three-dimensional circuit pattern, much like a engraving.

[0004] Photolithography is a key process in TFT manufacturing. Here, a thin layer of photoresist is applied to the TFT substrate. A photomask, which separates the areas where the electronic circuit pattern will be drawn from the rest, is then placed over the photoresist. When light is applied, the photoresist's properties change between the illuminated and unilluminated areas. This difference in solubility between the two regions is then exploited to remove the more soluble photoresist through a development process.

[0005] The deposited material remaining in the area where the photoresist has disappeared is removed through an etching process, and the deposited material remaining under the photoresist remains intact as it is protected by the photoresist.

[0006] As it became impossible to form fine patterns smaller than 50 nm using KrF (248 nm) and ArF (193 nm) light sources and general photoresists, a lithography process was recently developed that integrates many circuits in a narrower area using a short-wavelength light source and a chemically amplified DUV (Deep Ultraviolet) photoresist that responds to the short wavelength.

[0007] The short-wavelength light sources that are emerging include EUV (Extream Ultra-violet) (13 nm) light sources, ion beams, and X-rays. When the EUV light source is used, it is expected that it will be possible to design circuits of 0.1㎛ or less, and thus manufacture semiconductors 100 times faster and with 100 times more capacity than the currently used process.

[0008] Organic-based chemically amplified resist (CAR), a representative photoresist, has been used as a standard material up to the ArF generation, but with the introduction of EUV and process miniaturization, ① the photon absorption efficiency is very poor due to the low cross-section of carbon and oxygen, the main components of CAR, for EUV wavelength band photons, ② the uniformity and roughness characteristics deteriorate due to acid diffusion, and ③ the pattern collapse occurs during development due to the low mechanical strength of organic-based photoresists. Therefore, the need for the development of a new inorganic photoresist that can satisfy the RLS (Resolution, LER / LWR, Sensitivity) characteristics by ① having high photon absorbance at the EUV wavelength and ② having excellent mechanical strength and etching resistance has arisen.

[0009] Recently, inorganic photoresists utilizing liquid and vapor phase chemical reactions as a coating method are recognized globally as the only alternative technology for forming ultra-fine patterns. However, the development of core technologies for related materials, processes, and equipment remains inadequate. Therefore, to secure a lead in next-generation EUV patterning technology and ensure technological competitiveness, the development of inorganic photoresist materials and processes is essential. Research is therefore needed on compounds, compositions containing these materials, and thin film formation methods utilizing these materials.

[0010] The technical problem to be achieved by the present invention is to provide a precursor compound, a composition prepared with the compound together with a solvent, and a thin film formed through the composition to form a photoresist thin film having improved EUV photon absorption rate and excellent etching resistance.

[0011] The technical problems to be solved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by a person having ordinary skill in the technical field to which the present invention belongs from the description below.

[0012] In order to achieve the above technical task, one embodiment of the present invention provides a precursor compound comprising a plurality of metals and oxygen, wherein the oxygen is each bonded to three metals, at least one of the oxygens is connected to the same type of metals, the metal is bonded to the oxygen and a functional group, and one type of the metals is further bonded to an organic ligand.

[0013] In an embodiment of the present invention, a precursor compound comprising the following chemical formula 1 is provided.

[0014] [Chemical Formula 1]

[0015]

[0016] Here, M and M* are each independently a 5th period metal element, X is each independently a non-metal element of group 6 or 7, R1 and R2 are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof, L is a hydrolyzable ligand, and 0≤a≤5, 0≤d≤5, 0 <a+d<5, 1≤b≤5이다.

[0017] In an embodiment of the present invention, M and M* may each independently be a metal selected from Te, Sb, Sn, and In.

[0018] In an embodiment of the present invention, at least one of M and M* may include Te.

[0019] In an embodiment of the present invention, both M and M* may be Te.

[0020] In an embodiment of the present invention, R2 may include at least one tert-butyl group.

[0021] In an embodiment of the present invention, R2 may additionally include a methyl group (Me).

[0022] In an embodiment of the present invention, L may be selected from an ester group, an amine group, an amide group, an alkoxy group, a carbonyl group, an aldehyde group, and a carboxyl group.

[0023] In an embodiment of the present invention, the precursor compound may be any one selected from the following compound group 1.

[0024] [Compound group 1]

[0025]

[0026]

[0027]

[0028]

[0029] In order to achieve the above technical task, another embodiment of the present invention provides a precursor compound comprising a non-metallic element combined with three or more metals.

[0030] In an embodiment of the present invention, three to six metal and non-metal elements are included, at least one of the non-metal elements is bonded to three or more metals, at least one of the non-metal elements is connected to metals of the same type, and some of the metals can be bonded to the non-metal element or a functional group.

[0031]

[0032] In order to achieve the above technical task, another embodiment of the present invention provides a composition comprising the compound; and a solvent.

[0033] In an embodiment of the present invention, the solvent includes at least one of propylene glycol methyl ether acetate (PGMEA), n-butyl acetate (nBA), gamma-butyrolactone (gBL), isobutyl methyl isobutyl carbinol (MIBC), cyclohexanone, methyl ethyl ketone (MEK), ethyl lactate (EL), propylene glycol methyl ether (PGME), and tetramethylammonium hydroxide (TMAH).

[0034] In order to achieve the above technical task, another embodiment of the present invention provides a thin film comprising a precursor compound represented by the following chemical formula 1.

[0035] [Chemical Formula 1]

[0036]

[0037] Here, M and M* are each independently a 5th period metal element, X is each independently a non-metal element of group 6 or 7, R1 and R2 are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof, L is a hydrolyzable ligand, and 0≤a≤5, 0≤d≤5, 0 <a+d<5, 1≤b≤5이다.

[0038]

[0039] In an embodiment of the present invention, the thin film may have a contact angle with water of 60° or more.

[0040] In an embodiment of the present invention, when measuring infrared spectroscopy, 3200-3400 cm -1 In , the hydroxy peak may not exist.

[0041] According to an embodiment of the present invention, a composition including a precursor compound and a solvent can be spin-coated on a substrate and fired to form a thin film, and the thin film can have an increased photon absorption rate of EUV and excellent etching resistance.

[0042] The composition according to an embodiment of the present invention can exhibit excellent coating properties during spin coating. It should be understood that the effects of the present invention are not limited to the effects described above, but rather encompass all effects that can be inferred from the detailed description of the present invention or the composition of the invention described in the claims.

[0043] Figure 1 is an infrared spectroscopy (IR) analysis graph within the hydroxyl group (OH) peak range.

[0044] Hereinafter, the present invention will be described with reference to the attached drawings. However, the present invention can be implemented in various different forms and is therefore not limited to the embodiments described herein. In the drawings, irrelevant parts have been omitted for clarity of description, and similar parts have been designated with similar reference numerals throughout the specification.

[0045] Throughout the specification, when a part is said to be "connected (connected, contacted, or coupled)" to another part, this includes not only cases where it is "directly connected," but also cases where it is "indirectly connected" with another part in between. Furthermore, when a part is said to "include" a component, this does not exclude other components, but rather implies that it may include other components, unless otherwise specifically stated.

[0046] The terminology used herein is merely used to describe specific embodiments and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this specification, it should be understood that the terms "comprises" or "has" indicate the presence of a feature, number, step, operation, component, part, or combination thereof described in the specification, but do not exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

[0047] The term "substituted or unsubstituted" as used herein means a group that is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium; halogen; cyano group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amide group; amino group; carboxyl group; sulfonic acid group; sulfonamide group; phosphine oxide group; alkoxy group; alkylcarbonyl group; alkoxycarbonyl group; sulfonyloxy group; aryloxy group; alkylthioxy group; arylthioxy group; alkylsulfoxy group; arylsulfoxy group; silyl group; boron group; aryl group; and heteroaryl group, or a group that is unsubstituted or substituted with two or more substituents among the above-mentioned substituents linked to each other.

[0048] In this specification, examples of halogen include fluorine, chlorine, bromine or iodine.

[0049] In the present specification, the ester group may have the oxygen of the ester group replaced by a linear, branched, or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, the ester group may be a compound having the following structural formula, but is not limited thereto.

[0050]

[0051] The ester group can take the form of an ester by a carboxylic acid, and an example is as follows in the structural formula.

[0052]

[0053] At this time, R3 and R4 are each independently selected from a linear, branched, or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms, but are not limited thereto.

[0054] In the present specification, specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl (iPr), butyl, n-butyl, isobutyl, tert-butyl (tBu), sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohectylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, Examples thereof include, but are not limited to, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, and 5-methylhexyl. The alkyl group may be substituted or unsubstituted, and examples of the substituent when substituted are as described above.

[0055] In this specification, an alkoxy group is a functional group in which the aforementioned alkyl group is bonded to one end of an ether group (-O-), and the description of the aforementioned alkyl group may be applied to these groups, except that they are functional groups bonded to an ether group (-O-). For example, the alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkoxy group is not particularly limited, but may be 1 to 20 carbon atoms. Specifically, there are, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, cycloheptoxy, benzyloxy, p-methylbenzyloxy, etc. The alkoxy group may be substituted or unsubstituted, and when substituted, examples of the substituent are as described above.

[0056] In the present specification, the amine group may be selected from the group consisting of -NH2, a monoalkylamine group, a dialkylamine group, an N-alkylarylamine group, a monoarylamine group, a diarylamine group, an N-arylheteroarylamine group, an N-alkylheteroarylamine group, a monoheteroarylamine group, and a diheteroarylamine group, and the number of carbon atoms is not particularly limited, but may be 1 to 30. Specific examples of amine groups include, but are not limited to, a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, anthracenylamine group, a 9-methyl-anthracenylamine group, a diphenylamine group, a ditolylamine group, an N-phenylbiphenylamine group, an N-phenylnaphthylamine group, an N-biphenylnaphthylamine group, a ditolylamine group, an N-phenyltolylamine group, a triphenylamine group, an N-naphthylfluorenylamine group, an N-phenylphenanthrenylamine group, an N-biphenylphenanthrenylamine group, an N-phenylfluorenylamine group, an N-phenylterphenylamine group, an N-phenanthrenylfluorenylamine group, an N-biphenylfluorenylamine group, and the like. The amine group may be substituted or unsubstituted, and when substituted, examples of the substituent are as described above.

[0057] In the present specification, the amide group may be a group in which hydrogen, a straight-chain alkyl group having 1 to 30 carbon atoms, a branched-chain alkyl group having 3 to 30 carbon atoms, a cyclic alkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a combination thereof, is bonded to the nitrogen of the amide group.

[0058] In this specification, the contact angle refers to the contact angle of a substrate surface with respect to water. That is, the contact angle can be measured by using a video digital contact angle analyzer (KRUSS DSA100W) to measure the contact angle with respect to 3 μl of water (ultrapure water) on the outermost surface of a substrate or thin film, which is the contact angle measurement target, using the static contact angle method.

[0059] When a water droplet is dropped on a substrate on which a thin film including the composition of the present embodiment is deposited and the angle formed by the water droplet (contact angle with respect to water) is measured, the contact angle is measured to be 50° or more, specifically 60° or more, confirming that the hydrophobicity of the substrate surface is high.

[0060] In this specification, “” means a benzene ring.

[0061] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings.

[0062]

[0063] An embodiment of the present invention provides a precursor compound comprising a non-metallic element combined with three or more metals.

[0064] In this specification, “bond” may refer to both direct and indirect bonds. Furthermore, the type of bond is not limited to metallic bonds, coordinate bonds, ionic bonds, hydrogen bonds, covalent bonds, van der Waals bonds, and other specific bonds that can be formed.

[0065] The precursor compound may be a precursor compound comprising three to six metal and non-metal elements, wherein at least one of the non-metal elements is bonded to three or more metals, and at least one of the non-metal elements is linked to metals of the same type, and some of the metals may be bonded to the non-metal element or a functional group.

[0066] Some of the metals may be bonded to non-metal elements or functional groups, all of the metals may be bonded to non-metal elements or functional groups, and some or all of the metals may be bonded to non-metal elements and functional groups simultaneously.

[0067] The types of the above metals may be the same or different. The metal may be selected from the 5th period metallic elements, and specifically may be selected from Te, Sb, Sn, and In, but is not limited thereto. The non-metallic elements may each independently be non-metallic elements of Group 6 or Group 7, and specifically may be selected from O, S, N, and Se, and more specifically may be selected from O and S, and may all be the same, but are not limited thereto.

[0068]

[0069] In addition, a precursor compound is provided, which comprises a plurality of metals and oxygen, wherein the oxygen is each bonded to three metals, at least one of the oxygens is connected to the same type of metals, some of the metals are bonded to the oxygen or a functional group, and one type of the metals is further bonded to an organic ligand.

[0070] First, the precursor compound according to the present invention comprises a plurality of metals and non-metallic elements. The plurality of metals may be the same or different in type, and specifically, each may be independently selected from Te, Sb, Sn, and In. The non-metallic elements may each independently be non-metallic elements of Group 6 or Group 7, and specifically, may be selected from O, S, N, and Se, and more specifically, may be selected from O and S, and all may be the same.

[0071] The above nonmetallic elements are each bonded to three metals. At least one of them is bonded to metals (M) of the same type. The remaining nonmetallic elements are bonded to two metals (M) of the same type and one metal (M*) of a different type. If the metals are of the same type, multiple nonmetallic elements are all bonded to metals of the same type.

[0072] Some of the above metals may be bonded to the non-metallic elements or functional groups. The entire metal may also be bonded to the non-metallic elements or functional groups. Some of the above metals may be bonded to the non-metallic elements and functional groups. The functional groups may be organic ligands having 1 to 20 carbon atoms or combinations thereof.

[0073] One of the above metals is further bonded to an organic ligand. The metal further bonded to the organic ligand is bonded to the organic ligand, a functional group, and three non-metallic elements.

[0074] The above precursor compound has a structure represented by the following chemical formula 1 and can be represented by the following chemical formula 1.

[0075] [Chemical Formula 1]

[0076]

[0077] Here, M and M* are each independently a 5th period metal element, X is each independently a non-metal element of group 6 or 7, R1 and R2 are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof, L is a hydrolyzable ligand, and 0≤a≤5, 0≤d≤5, 0 <a+d<5, 1≤b≤5이다.

[0078] Specifically, the above M and M* are each independently a metal selected from Te, Sb, Sn, and In. More specifically, the above M may be Te or Sn. When M is Sn, M* may be Te, when M is Sn, M* may be Sn, when M is Te, M* may be Sn, and when M is Te, M* may be Te.

[0079] At least one of the above M and M* may include Sn. At least one of the above M and M* may include Te.

[0080] Each of the above Xs is independently a non-metallic element of group 6 or group 7. Specifically, X may be selected from O, S, N, Se, and more specifically, may be selected from O and S, and all Xs may be the same.

[0081] The above R1 and R2 are each independently selected from hydrogen, a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

[0082] When b is 2 or more, R2 may be independently selected from two or more of hydrogen, a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

[0083] Specifically, R1 may be selected from Me, iPr, tBu, CH2CHCH-, C6H5CH2-, but is not limited thereto. More specifically, R1 may be selected from iPr, tBu, or CH2CHCH-.

[0084] The above R2 may be selected from Me, Me, Me or Me, tBu, Me or nBu, nBu, nBu or tBu, but is not limited thereto. The above R2 may include at least one tBu, and may additionally include a methyl group. Specifically, R2 may be selected from Me, tBu, Me or tBu, but is not limited thereto.

[0085] Additionally, R1 or R2 may include a halogenated alkyl group or a branched alkyl group.

[0086] An alkenyl group is a straight-chain or branched-chain aliphatic hydrocarbon group, and refers to an aliphatic unsaturated alkenyl group containing one or more double bonds.

[0087] An aryl group is a substituent in which all atoms of a cyclic substituent have p-orbitals, and these p-orbitals form conjugation, and may include a monocyclic or fused ring polycyclic (i.e., a ring that shares adjacent pairs of carbon atoms) functional group.

[0088] In the case of aryl groups, the effect may be similar to that of linear alkyls.

[0089] The above alkyl group, alkenyl group or aryl group may be halogenated. Specifically, -(CH2) n CF3, -(CH2) n I, -(CH2) n It has the same structure as CHCH2, but this is only a limited example and is not limited thereto.

[0090] The above L is a hydrolyzable ligand selected from an ester group, an amine group, an amide group, an alkoxy group, a carbonyl group, an aldehyde group, and a carboxyl group.

[0091] Specifically, L can be selected from an amine group, an ester group, and an alkoxy group.

[0092] When L is an ester group or an alkoxy group, it may have excellent stability due to low reactivity with moisture in the air.

[0093] Specifically, L can be propionate or -OC(CH3)2Et.

[0094] Also, in the above chemical formula 1, 0≤a≤5, 0≤d≤5, 0 <a+d<5, 1≤b≤5이다.

[0095] Specifically, a can be an integer from 0 to 5, and d can be an integer from 0 to 5. Specifically, when a is 0, d can be an integer from 1 to 4, and when d is 0, a can be an integer from 1 to 4. Specifically, the sum of a and d can be 4. When a is 0, d can be 4, and when a is 1, d can be 3.

[0096] As a specific example, the precursor compound according to an embodiment of the present invention may be any one selected from the following compound group 1.

[0097] [Compound group 1]

[0098]

[0099]

[0100]

[0101]

[0102] Another embodiment of the present invention provides a composition comprising the compound and a solvent.

[0103] The above composition may include two or more kinds of precursor compounds including non-metallic elements combined with three or more metals.

[0104] When forming the composition, the compound may be included together with the solvent at a concentration of 1 to 20 wt%.

[0105] The solvent includes, but is not limited to, one or more of propylene glycol methyl ether acetic acid (1-methoxy-2-propanol acetate, PGMEA), n-butyl acetate (nBA), gamma-butyrolactone (gBL), isobutyl methyl carbinol (MIBC), cyclohexanone, methyl ethyl ketone (MEK), ethyl lactate (EL), propylene glycol methyl ether (PGME), and tetramethylammonium hydroxide (TMAH).

[0106] Specifically, the solvent may be selected from PGMEA or isobutyl methyl carbinol (MIBC).

[0107] Propylene glycol methyl ether acetic acid (PGMEA) is a key raw material used in the semiconductor EUV (extreme ultraviolet) process. It is manufactured as a thinner for semiconductors and can play a role in washing away photosensitive material (photoresist) that has adhered to areas where extreme ultraviolet light sensitivity reaction does not occur during the EUV exposure process.

[0108] Isobutyl methyl carbinol (MIBC) is 4-methyl-2-propanol and can be used primarily as a foaming agent in the production of mineral flotation and lubricant oil additives such as zinc dithiophosphate.

[0109] N-butyl acetate (nBA) can also be used as a solvent in photoresist compositions.

[0110] Gamma-butyrolactone (gBL) is a hygroscopic, colorless, water-miscible liquid that can be used as an industrial chemical intermediate and solvent.

[0111] Methyl Ethyl Ketone (MEK) is a strong solvent that can be commonly used as a negative photoresist remover.

[0112] Ethyl lactate (EL) is biodegradable and can be used as a solvent in photoresist processes.

[0113] Propylene glycol methyl ether (PGME) is an organic solvent with a wide range of industrial and commercial applications.

[0114] Tetramethylammonium hydroxide (TMAH) can be used as a basic solvent in the development of acidic photoresists in photolithography processes and is very effective in stripping photoresists.

[0115]

[0116] A thin film can be formed through a method including a step of coating a composition represented by the above chemical formula 1 on a substrate and then firing it.

[0117] The step of treating the substrate surface by washing and flowing the substrate surface prior to the coating step may further be included.

[0118] Afterwards, the composition according to the present invention can be coated on the substrate.

[0119] An embodiment according to the present invention can provide a pattern forming method including the steps of: forming a photoresist film by coating the composition on a substrate; exposing the photoresist film with an EUV light source; and developing the exposed photoresist film to form a photoresist pattern.

[0120] The content regarding the above photoresist composition includes the content described above with respect to the other embodiments.

[0121] The above coating method may be a wet and / or dry coating method. The wet coating method may be spin coating, and the dry coating method may use CVD, ALD deposition, etc., but is not limited thereto. In addition, spray coating, dip coating, knife-edge coating, or printing processes may be used, but are not limited thereto.

[0122] For spin coating, it can be performed at 1000 rpm to 2000 rpm for 10 seconds to 1 minute.

[0123] The above pattern forming method comprises, for example, applying the photoresist film using a spinner or the like, exposing the photoresist film with a high-energy EUV ray having a wavelength of 300 nm or less using a predetermined photomask, and developing the exposed photoresist film with a conventional developer (for example, an alkaline aqueous solution such as a tetramethylammonium hydroxide aqueous solution of 0.1 wt% or more and 10 wt% or less). Examples of the developer include, but are not limited to, tetramethylammonium hydroxide, methyl isobutyl carbinol, and 4-methyl-2-propanol.

[0124] Specifically, the pattern forming method can form a pattern by going through the steps of applying the above-described photoresist composition onto a silicon wafer substrate, heating the applied substrate to form a resist thin film, exposing the resist thin film using a selected high-energy exposure source, desorbing an acid labile group in a polymer resin by an acid generated at an exposed portion, and developing the resist thin film, the solubility of which has been changed, with the developer.

[0125] Optionally, the photoresist composition can form a pattern with excellent performance even when a high-energy ray having a general wavelength of 300 nm or less is applied as an exposure light source in addition to the extreme ultraviolet (EUV) light. For example, the high-energy ray having a wavelength of 300 nm or less may be ultraviolet, ultraviolet, electron, X-ray, excimer laser, γ-ray, or synchrotron radiation.

[0126] In addition, for forming fine patterns of 70 nm or less, it is preferable to use an exposure device equipped with a source of high-energy short-wavelength rays such as an ArF excimer laser, a KrF excimer laser, or an EUV.

[0127] The above substrate can be a circular silicon wafer with a diameter of 8 or 12 inches, which can be used as a substrate for thin film deposition.

[0128] More specifically, the high-energy light source may be EUV with a wavelength of 13.5 nm, and may be selected from KrF with a wavelength of 248 nm, ArF with a wavelength of 193 nm, or electron beam (e-beam) as needed.

[0129] In addition, the above photoresist pattern can be formed into a thin film pattern by performing an etching process using a well-known method.

[0130] The photoresist pattern formed by the above method may have a line width of 5 to 100 nm and a line width roughness of 50 nm or less. In addition, the photoresist pattern may have a line width of 5 to 50 nm, and specifically, may have a line width of 20 to 30 nm.

[0131]

[0132] Since the composition has a large number of alkyl groups R1 and R2 bonded to the metal, the alkyl group bond is broken during EUV exposure and bonding with the metal is advantageous, thereby improving the coatability.

[0133] The solvent portion is then evaporated through a calcination step. The calcination can be performed at a temperature of 300° or less for 5 minutes or less.

[0134]

[0135] Another embodiment of the present invention provides a thin film comprising the above chemical formula 1.

[0136] The above thin film has a contact angle with water of 60° or more.

[0137] The presence of R2 is essential for EUV photoreaction. The contact angle with water refers to the angle between the water droplet and the solid interface when water is dropped on the solid. A small contact angle indicates high wettability and hydrophilicity, while a large contact angle indicates low wettability and hydrophobicity.

[0138] In general, the contact angle of a metal oxide film is hydrophilic and lower than 50°. However, the thin film according to the present invention exhibits low wettability, hydrophobicity, with a contact angle of 60° or higher.

[0139] Since the photoresist thin film according to the present invention does not have hydroxo, when measuring infrared spectroscopy, it is 3200-3400 cm -1 In this case, a hydroxy peak (OH peak) may not exist. This means that the photoresist thin film according to the present invention exhibits hydrophobicity.

[0140]

[0141] Hereinafter, synthetic examples and examples are presented to aid understanding of the invention. However, the following synthetic examples and examples are intended only to illustrate the present invention and are not intended to limit the invention to these examples.

[0142]

[0143] - Compound synthesis

[0144] <Synthesis Example 1> Synthesis of a compound represented by Chemical Formula 2

[0145] [Chemical Formula 2]

[0146]

[0147] After mixing the first precursor (MeSn(OCOEt)3) and ethanol (EtOH) at a low temperature (0 to 10°C), water (H2O) was added, and the mixture was stirred at room temperature (25°C) for 18 hours. Thereafter, the second precursor (nBu3Sn(NMe2)) was added, stirred for 18 hours, and the solvent (ethanol) and byproduct (dimethylamine) were removed under reduced pressure to obtain the compound represented by the chemical formula 2 in a yield of 70% or more.

[0148]

[0149] <Synthesis Examples 2 to 22>

[0150] Synthesis Examples 2 to 19 differ from Synthesis Example 1 only in the type of precursor, and were synthesized using the same method as Synthesis Example 1, and were obtained in a yield of 70% or more.

[0151] Synthetic examples 20 to 22 were synthesized in the same manner as the above synthetic example 1, except that hydrogen sulfide (H2S) was used instead of water (H2O), and were obtained in a yield of 70% or more.

[0152] Synthesis Example 23 is a mixture obtained by simply mixing the compound represented by chemical formula 3 synthesized in Synthesis Example 2 and the compound represented by chemical formula 17 synthesized in Synthesis Example 16 at room temperature.

[0153] The types of the first precursor and the second precursor used in each synthesis example and the chemical formula of each synthesis example are shown in Table 1 below.

[0154]

[0155] Synthesis Example Chemical Formula 1 Precursor System 2 Precursor Structure 12MeSn(OCOEt)3nBu3Sn(NMe2) 23MeSn(OCOEt)3tBuMe2Sn(NMe2) 34MeSn(OCOEt)3tBuSn(NMe2) 45iPrSn(OCOEt)3nBu3Sn(NMe2) 56iPrSn(OCOEt)3tBuMe2Sn(NMe2) 67iPrSn(OCOEt)3tBuSn(NMe2) 78tBuSn(OCOEt)3nBu3Sn(NMe2) 89tBuSn(OCOEt)3tBuMe2Sn(NMe2) 910tBuSn(OCOEt)3tBuSn(NMe2) 1011C3H4Sn(OCOEt)3tBuMe2Sn(NMe2) 1112C3H4Sn(OCOEt)3tBuSn(NMe2) 1213C7H7(OCOEt)3tBuMe2Sn(NMe2) 1314C7H7(OCOEt)3tBuSn(NMe2) 1415tBuSn(OC(CH3)2Et)3tBuMe2Sn(NMe2) 1516tBuSn(OC(CH3)2Et)3tBuSn(NMe2) 1617Sn(OCOEt)3tBuMe2Sn(NMe2) 1718MeTe(OCOEt)3tBuMe2Sn(NMe2) 1819MeSn(OCOEt)3tBuMe2Te(NMe2) 1920MeTe(OCOEt)3tBuMe2Te(NMe2) 2021MeSn(OCOEt)3nBu3Sn(NMe2) 2122MeSn(OCOEt)3tBuSn(NMe2) 2223Sn(OCOEt)3tBuMe2Sn(NMe2)

[0156]

[0157] The NMR peak data of the synthetic example are shown in Table 2 below.

[0158] Synthesis ExampleNMR Peak(1)1H-NMR (C6D6) : δ 0.64 (s, 9H), δ 0.97 (t, 27H), δ 1.01 (t, 9H), δ 1.28 (m, 24H), δ 1.47 (m, 24H), δ 1.68 (t, 24H), δ 2.21 (q, 6H).(2)1H-NMR (C6D6) : δ 0.67 (s, 9H), δ 0.71 (s, 18H), δ 1.08 (t, 9H), δ 1.40 (s, 27H), δ 2.19 (q, 6H).(3)1H-NMR (C6D6) : δ 0.69 (s, 9H), δ 1.18 (t, 9H), δ 1.44 (s, 27H), δ 2.11 (q, 6H).(4)1H-NMR (C6D6) : δ 0.85 (t, 27H), δ 1.01 (d, 18H), δ 1.11 (t, 9H), δ 1.24 (m, 24H), δ 1.38 (m, 24H), δ 1.70 (t, 24H), δ 2.01 (m, 3H), δ 2.22 (q, 6H).(5)1H-NMR (C6D6) : δ 0.69 (s, 18H), δ 1.03 (d, 18H), δ 1.18 (t, 9H), δ 1.42 (s, 27H), δ 2.10 (m, 3H), δ 2.17 (q, 6H).(6)1H-NMR (C6D6) : δ 1.05 (d, 18H), δ 1.21 (t, 9H), δ 1.40 (s, 27H), δ 2.11 (m, 3H), δ 2.13 (q, 6H).(7)1H-NMR (C6D6) : δ 0.93 (t, 27H), δ 1.11 (t, 9H), δ 1.28 (m, 24H), δ 1.32 (s, 27H), δ 1.43 (m, 24H), δ 1.58 (t, 24H), δ 2.18 (q, 6H).(8)1H-NMR (C6D6) : δ 0.65 (s, 18H), δ 1.16 (t, 9H), δ 1.38 (s, 27H), δ 1.42 (s, 27H), δ 2.15 (q, 6H).(9)1H-NMR (C6D6): δ 1.13 (t, 9H), δ 1.35 (s, 27H), δ 1.41 (s, 27H), δ 2.23 (q, 6H).(10)1H-NMR (C6D6) : δ 0.63 (s, 18H), δ 1.15 (t, 9H), δ 1.41 (s, 27H), δ 1.87 (d, 6H), δ 2.11 (q, 6H), δ 4.72 (m, 6H), δ 5.81 (m, 3H).(11)1H-NMR (C6D6) : δ 1.07 (t, 9H), δ 1.40 (s, 27H), δ 1.79 (d, 6H), δ 2.13 (q, 6H), δ 4.78 (m, 6H), δ 5.88 (m, 3H).(12)1H-NMR (C6D6) : δ 0.67 (s, 18H), δ 1.13 (t, 9H), δ 1.41 (s, 27H), δ 2.20 (q, 6H), δ 2.63 (s, 6H), δ 7.31 (m, 15H).(13)1H-NMR (C6D6) : δ 1.08 (t, 9H), δ 1.45 (s, 27H), δ 2.24 (q, 6H), δ 2.67 (s, 6H), δ 7.28 (m, 15H).(14)1H-NMR (C6D6) : δ 0.62 (s, 18H), δ 0.92 (t, 9H), δ 1.21 (s, 18H), δ 1.32 (s, 27H), δ 1.36 (q, 6H), δ 1.42 (s, 27H).(15)1H-NMR (C6D6) : δ 0.89 (t, 9H), δ 1.24 (s, 18H), δ 1.40 (s, 27H), δ 1.46 (q, 6H), δ 1.49 (s, 27H).(16)1H-NMR (C6D6) : δ 0.36 (s, 18H), δ 1.09 (t, 9H), δ 1.18 (s, 27H), δ 2.28 (q, 6H).(17)1H-NMR (C6D6) : δ 0.69 (s, 9H), δ 0.75 (s, 18H), δ 1.11 (t, 9H), δ 1.35 (s, 27H), δ 2.14 (q, 6H).(18)1H-NMR (C6D6) : δ 0.59 (s, 9H), δ 0.73 (s, 18H), δ 1.08 (t, 9H), δ 1.42 (s, 27H), δ 2.21 (q, 6H).(19)1H-NMR (C6D6): δ 0.62 (s, 9H), δ 0.71 (s, 18H), δ 1.14 (t, 9H), δ 1.38 (s, 27H), δ 2.17 (q, 6H).(20)1H-NMR (C6D6): δ 0.64 (s, 9H), δ 0.73 (s, 18H), δ 1.18 (t, 9H), δ 1.43 (s, 27H), δ 2.17 (q, 6H). (21)1H-NMR (C6D6): δ 0.69 (s, 9H), δ 1.21 (t, 9H), δ 1.42 (s, 27H), δ 2.10 (q, 6H).(22)1H-NMR (C6D6): δ 0.67 (s, 18H), δ 1.09 (t, 9H), δ 1.40 (s, 27H), δ 2.21 (q, 6H).(23)1H-NMR (C6D6): δ 0.36 (s, 18H), δ 0.67 (s, 9H), δ 0.71 (s, 18H), δ 1.08 (t, 18H), δ 1.18 (s, 27H), δ 1.40 (s, 27H), δ 2.19 (q, 6H), δ 2.28 (q, 6H).

[0159] The synthetic yield (%) of the synthetic example is shown in Table 3 below.

[0160] Synthesis yield (%) (1) 71 (2) 74 (3) 72 (4) 81 (5) 79 (6) 76 (7) 73 (8) 72 (9) 77 (10) 71 (11) 79 (12) 80 (13) 81 (14) 74 (15) 76 (16) 75 (17) 71 (18) 76 (19) 77 (20) 79 (21) 73 (22) 72

[0161]

[0162] <Examples 1 to 22>

[0163] Compounds represented by chemical formulas 2 to 23 synthesized in Synthesis Examples 1 to 22 were dissolved in PGMEA or isobutyl methyl carbinol (MIBC) at a concentration of 2 to 5 wt%, mixed, and then filtered to prepare a composition for semiconductor photoresist.

[0164]

[0165] <Example 23>

[0166] Example 23 is a mixture of Synthesis Example 23 and a solvent.

[0167]

[0168] <Comparative Example 1>

[0169] After mixing a tin precursor and ethanol (EtOH) at room temperature, water (H2O) was added and stirred for 18 hours, and the solvent was removed under reduced pressure to obtain a compound containing an alkyl tin-oxo hydroxo trimer. A photoresist composition was formed in the same manner as in Examples 1 to 19.

[0170]

[0171] <Experimental Example>

[0172] -Storage stability evaluation

[0173] When a composition made through synthesis is left at room temperature (15 to 25℃) for a certain period of time, the degree of precipitation / gelation is observed with the naked eye, and the degree of precipitation / gelation is indicated in Table 4 as follows: No precipitation / gelation for up to 6 months: ◎, No precipitation / gelation for up to 3 months: O, Up to 1 month: △, Within 1 week: X.

[0174]

[0175] The exposure characteristics of the resist pattern were evaluated using the following method, and the results are shown in Table 4.

[0176]

[0177] -Coating evaluation

[0178] A composition according to the above synthesis example was spin-coated at 1,500 rpm for 30 seconds on a SiON substrate on which a hard mask was formed, and baked at 180° C. for 120 seconds to form a thin film.

[0179] The thickness of the thin film after coating and baking was measured using ellipsometry, and the measured thickness was approximately 20 to 30 nm.

[0180]

[0181] - Sensitivity measurement

[0182] After forming the above thin film, it was exposed to EUV radiation and baked at 180°C for 120 seconds (post-exposure bake, PEB). The baked thin film was immersed in a developer (PGMEA) and washed to form a negative-tone image. The residual resist thickness was measured using a polarimetric method, and the dose per unit gel (Dg) for each resist type is shown in Table 4 below.

[0183]

[0184] - Infrared spectroscopy (IR) analysis

[0185] The formed thin film was analyzed by infrared spectroscopy (IR) using a Bruker Vertex70 device at room temperature (typically, 15 to 25°C), and the range of the hydroxy peak (wavelength 3200 cm -1 3400cm inland -1 ) to check whether a peak appears within the sample, and the presence or absence of a hydroxy peak is expressed as O or X.

[0186] Referring to Table 4 and Figure 1, the solid line in Figure 1 represents Example 2, and the dotted line represents Comparative Example 1. As a result of IR analysis, in the case of the photoresist thin film according to the present invention, the range of the hydroxy peak (wavelength 3256 cm -1 ) can be confirmed that no peak appears within the sample. This indicates that the hydroxyl group has been removed.

[0187]

[0188] [Correction pursuant to Rule 91, August 13, 2025] [Table 4]

[0189] Here, if the contact angle is 60 or more, it is indicated as O, and if it is less than 50, it is indicated as X. In the case of the substrate on which the coating film was not formed, the angle was measured to be less than 50°. As shown in Table 4 above, it can be confirmed that the polarity of the substrate surface is relatively reduced (hydrophobicity) after the thin film is formed in the example, compared to the silicon substrate before the thin film is formed.

[0190] As a result of the evaluation, it can be confirmed that when the compositions of Examples 1 to 23 were used, the sensitivity was superior to that of Comparative Example 1, which used only a single precursor. Examples 18 to 20, which included Te among the metals, had superior sensitivity to that of Example 2, which included only Sn among the metals.

[0191] It can be confirmed that the coating film C / A value is 60 or higher. That is, the coating film exhibits hydrophobicity, and it can be confirmed that the compound of [chemical formula 1] does not contain a hydroxyl group, which can be confirmed through Figure 1. Since there is no hydroxyl group in the composition, there is little possibility of reaction with external moisture when stored in the form of the composition, so the stability is excellent. The reaction between external moisture and hydroxyl groups causes deformation of the material, which causes storage stability issues, but the material of the present invention has a structure without a hydroxyl group, so relatively improved storage stability can be expected.

[0192]

[0193] When forming a thin film according to the present invention, the metal density within the compound molecule of [Chemical Formula 1] is high relative to the thickness, which is advantageous for improving sensitivity. Since there are many R1 and R2 bonded to the metal, the alkyl group bond is broken during EUV exposure, and bonding with the metal is advantageous.

[0194] It is possible to use a precursor with excellent absorption efficiency to absorb EUV photons while simultaneously acting as a photoresist or hard mask with excellent etching resistance, and by introducing a metal with high absorption within the resist thin film, that is, capable of emitting a large amount of secondary electrons through EUV absorption, an EUV resist with high throughput and reduced shot noise can be secured. By reducing shot noise, the irregularity of the overall line width of the photoresist pattern (LWR) or the extent to which the edge of the actually formed pattern deviates from the edge of the target pattern (LER) can be improved.

[0195] Since there are no OH groups in the composition, it exhibits hydrophobicity and thus has excellent storage stability.

[0196] As a result, the present invention can contribute to the production of ultra-fine semiconductor devices using EUV while implementing inorganic photoresist materials and process technology.

[0197]

[0198] The foregoing description of the present invention is for illustrative purposes only, and those skilled in the art will readily appreciate that the present invention can be readily modified into other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single entity may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined manner.

[0199] The scope of the present invention is indicated by the claims described below, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

Claims

A precursor compound comprising a non-metallic element combined with three or more metals. In the first paragraph, Contains 3 to 6 metal and non-metal elements, At least one of the above non-metallic elements is combined with three or more metals, At least one non-metallic element among them is linked to a metal of the same type, A precursor compound, wherein some of the above metals can be combined with the above non-metal elements or functional groups. In the first paragraph, A precursor compound comprising the following chemical formula 1: [Chemical Formula 1] Here, M and M* are each independently a 5th period metallic element, X is independently a non-metallic element of group 6 or group 7, R1 and R2 are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof, L is a hydrolyzable ligand, 0≤a≤5, 0≤d≤5, 0 <a+d<5, 1≤b≤5이다. In the third paragraph, A precursor compound wherein the above M and M* are each independently a metal selected from Te, Sb, Sn and In. In the third paragraph, A precursor compound, wherein at least one of the above M and M* comprises Te. In the third paragraph, A precursor compound wherein both M and M* are Te. In the third paragraph, A precursor compound wherein the above R2 contains at least one tert-butyl group (tBu). In paragraph 7, The above R2 is a precursor compound further comprising a methyl group (Me). In the third paragraph, A precursor compound wherein the above L is selected from an ester group, an amine group, an amide group, an alkoxy group, a carbonyl group, an aldehyde group, and a carboxyl group. In the first paragraph, The above precursor compound is selected from the following compound group 1: [Compound group 1] The compound of paragraph 1; and A composition comprising a solvent. In Article 11, The composition comprises two or more kinds of precursor compounds including non-metallic elements combined with three or more metals. In Article 11, A composition wherein the solvent comprises at least one of propylene glycol methyl ether acetate, n-butyl acetate, gamma-butyrolactone, isobutyl methyl isobutyl carbinol, cyclohexanone, methyl ethyl ketone, ethyl lactate, propylene glycol methyl ether, and tetramethylammonium hydroxide. A thin film comprising a compound represented by the following chemical formula 1. [Chemical Formula 1] Here, M and M* are each independently a 5th period metal element, X is each independently a group 6 or group 7 non-metal element, R1 and R2 are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof, L is a hydrolyzable ligand, and 0≤a≤5, 0≤d≤5, 0 <a+d<5, 1≤b≤5이다. In Article 14, The above thin film is a thin film having a contact angle with water of 60° or more. In Article 14, 3200cm when measuring infrared spectroscopy -1 3400cm inland -1 A thin film in which no hydroxy peak appears in the range.

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