Highly transparent resin composition comprising an insoluble zirconium oxide compound and a polymer for carbon hard mask

Abstract

The present invention relates to a high transparent resin composition which can be applied in a semiconductor etching process or the like, and more particularly, to a high transparent resin composition comprising an insoluble zirconium oxide compound and a polymer for carbon hard mask, which can improve coating property, transparency and etching property in a semiconductor etching process, while suppressing generation of fume.

Description

Technical Field

[0001] This invention relates to a highly transparent resin composition that can be used in semiconductor etching processes, and more specifically, to a highly transparent resin composition comprising an insoluble zirconium oxide compound and a polymer for carbon hard masks, which can improve the coatability, transparency and etching performance in semiconductor etching processes, while suppressing the generation of fume. Background Technology

[0002] In the photolithography process of semiconductor manufacturing, a hard mask layer is further formed between the material layer to be etched and the photoresist layer to effectively etch fine patterns. The hard mask acts as an intermediate film for transferring the pattern of the photoresist onto the material layer.

[0003] Existing photolithography processes utilize either organic polymer resins or amorphous carbon layers (ACLs) as the materials for hard masks. Compared to processes that deposit amorphous carbon layers (ACLs), using organic polymer resins is preferred in terms of process efficiency, hence the recent adoption of organic hard masks using organic polymer resins. On the other hand, although there are many types of existing organic hard mask materials, their etching performance at the same thickness is lower than that of amorphous carbon layers (ACLs), which are primarily used on substrates. Therefore, processes requiring greater thicknesses than those using amorphous carbon layers (ACLs) are needed to achieve the desired etching performance.

[0004] In the patterning process used to prepare highly integrated semiconductor materials in recent years, in order to form thick circuit patterns, the thickness of organic hard mask materials with low etching performance becomes thicker. As the thickness increases, the aspect ratio between the height and the bottom increases, which leads to pattern collapse or the photoresist profile cannot maintain the ideal shape, resulting in a significant change in etch bias.

[0005] Therefore, in addition to existing organic polymers, various inorganic materials (e.g., silica, carbon nanotubes (CNTs), zirconium oxide, etc.) have been used to prepare and evaluate hard mask compositions. However, when using inorganic materials, a dispersant needs to be added separately to ensure uniform dispersion within the hard mask material. If only inorganic materials are used for coating, uniform thickness cannot be maintained when the thickness increases above 3000 Å. Furthermore, with increasing thickness, transparency decreases (haze increases), making alignment with the underlying film difficult, thus hindering subsequent processes. Moreover, the application of dispersants to improve coatability and uniform coating onto the substrate, as well as the use of thermal acid generators (TAGs), presents problems of generating fumes and outgassing that can contaminate equipment in existing high-temperature processes above 300°C. Therefore, technologies to address these issues need to be developed. Summary of the Invention

[0006] Technical issues The purpose of this invention is to provide a highly transparent resin composition that, by utilizing an insoluble zirconium oxide compound, allows for easy mixing with polymers used in carbon hard masks without the need for a dispersant, thereby solving the problems of fume and outgas generation caused by dispersants and hot acid generators, and improving the durability, transparency, and etching properties of hard masks.

[0007] The objectives of this invention are not limited to those described above. Other objectives and advantages of the invention not mentioned herein will be understood through the following description and will become clearer through embodiments of the invention. Furthermore, it will be readily recognized that the objectives and advantages of this invention can be achieved by the means and combinations thereof pointed out in the claims.

[0008] Technical solution To achieve the aforementioned objective, according to one embodiment of the present invention, a highly transparent resin composition for hard masks is provided, comprising: a polymer for carbon hard masks; a nanoscale insoluble zirconium oxide compound with an average diameter of 1 nm to 50 nm; and an organic solvent.

[0009] The polymer used for the carbon hard mask may include polymers represented by the following chemical formula 1 or chemical formula 2.

[0010] Chemical Formula 1:

[0011] Chemical formula 2:

[0012] In Formula 1, R1 atoms may be the same or different from each other, and are independently selected from hydrogen, hydroxyl, C1-C10 alkyl, C6-C10 aryl, C3-C10 allyl, and halogen atoms. In chemical formula 2, the R3 groups may be the same or different from each other, and each group is independently selected from hydrogen, hydroxyl, and -C. p H 2p In O, p is an integer from 1 to 7. The R2 groups of chemical formula 1 and / or chemical formula 2 are the same or different from each other, and are any of the compound groups represented by chemical formulas (1-1) to (1-5) below. n and m are repeating units, each being an independent integer from 1 to 100.

[0013] Chemical formula 1-1:

[0014] Chemical formulas 1-2:

[0015] Chemical formulas 1-3:

[0016] Chemical formulas 1-4:

[0017] Chemical formulas 1-5:

[0018] In the chemical formula 1, one or more of R2 contains compound groups represented by chemical formulas 1-5.

[0019] In the chemical formula 2, one or more of R2 contains compound groups represented by chemical formulas 1-5.

[0020] The weight-average molecular weight of the polymer used for the carbon hard mask can be between 2000 and 5000.

[0021] The insoluble zirconium oxide compound can be a compound obtained by surface treatment of zirconium oxide with a hydrophobic surface treatment agent.

[0022] The hydrophobic surface treatment agent can be a silane coupling agent containing alkoxy groups.

[0023] The silane coupling agent can be selected from alkyltrimethoxysilanes and alkyltriethoxysilanes represented by the following chemical formula 3.

[0024] Chemical formula 3: Si(X)3(Y) In the chemical formula 3, X is a methoxy or ethoxy group, and Y is a C1-C7 straight-chain alkyl group.

[0025] When the high-transparency resin composition for hard masks is 100% by weight, the content of the insoluble zirconium oxide compound can be from 0.1% by weight to 40% by weight.

[0026] The organic solvent may include one or more of tetrahydronaphthalene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, propylene glycol n-propyl ether, dimethylformamide, γ-butyrolactone, ethoxyethanol, methoxyethanol, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate.

[0027] According to another embodiment of the present invention, a method for patterning a semiconductor device can be provided, the method using a highly transparent resin composition for hard masks according to an embodiment of the present invention.

[0028] The weight-average molecular weight of the polymer used for the carbon hard mask can be between 2000 and 5000.

[0029] The insoluble zirconium oxide compound can be a compound obtained by surface treatment of zirconium oxide with a hydrophobic surface treatment agent.

[0030] The hydrophobic surface treatment agent can be a silane coupling agent containing alkoxy groups.

[0031] The silane coupling agent can be selected from alkyltrimethoxysilanes and alkyltriethoxysilanes represented by the following chemical formula 3.

[0032] Chemical formula 3: Si(X)3(Y) In the chemical formula 3, X is a methoxy or ethoxy group, and Y is a C1-C7 straight-chain alkyl group.

[0033] When the high-transparency resin composition for hard masks is 100% by weight, the content of the insoluble zirconium oxide compound can be from 0.1% by weight to 40% by weight.

[0034] The organic solvent may include one or more of tetrahydronaphthalene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, propylene glycol n-propyl ether, dimethylformamide, γ-butyrolactone, ethoxyethanol, methoxyethanol, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate.

[0035] According to another embodiment of the present invention, a method for patterning a semiconductor device can be provided, the method using a highly transparent resin composition for hard masks according to an embodiment of the present invention.

[0036] The effects of the invention According to the high-transparency resin composition of the present invention, an insoluble zirconium oxide compound can be easily mixed with a polymer for carbon hard masking without a dispersant.

[0037] The high-transparency resin composition of the present invention, since it does not contain dispersants and hot acid generators, can avoid the decrease in coatability, decrease in transparency, generation of fumes and gas release caused by dispersants, thereby preventing equipment contamination and improving process efficiency by shortening process time and reducing maintenance costs.

[0038] The high transparency of the resin composition of the present invention allows subsequent processes to proceed smoothly due to its high transparency, and can significantly improve etching characteristics even at a high thickness of 3000 Å or more.

[0039] The high-transparency resin composition of the present invention can achieve excellent planarization and gap-filling properties.

[0040] The effects of this invention are not limited to those described above, and other effects not mentioned can be clearly understood by those skilled in the art from the description of the scope of protection of the invention. In addition to the effects described above, the effects of this invention will be described together with the specific embodiments described below.

[0041] Best practice The aforementioned objectives, features, and advantages will be described in detail below with reference to the specification, thereby enabling those skilled in the art to readily implement the technical concept of this invention. In describing this invention, if it is determined that a detailed description of publicly known techniques related to this invention might unnecessarily obscure the essence of the invention, such detailed description will be omitted.

[0042] In the course of describing this specification, if it is determined that a detailed description of relevant prior art may unnecessarily obscure the essence of this specification, its detailed description will be omitted.

[0043] In this specification, when using terms such as "including," "having," "containing," "setting," or "possessing" to describe structural elements, other parts may be added unless "only" is used. When a structural element is described in the singular, it includes the plural form unless otherwise explicitly stated.

[0044] In this specification, when any element is "on" another element, this includes not only the case where any element is in contact with another element, but also the case where there are other elements between the elements.

[0045] In this specification, the mean diameter of the nanoscale particles is obtained by measuring the mean diameter of the nanocrystals using dynamic light scattering (DLS).

[0046] The present invention will now be described in more detail.

[0047] According to one embodiment of the present invention, a highly transparent resin composition for hard masks can be provided, comprising: a polymer for carbon hard masks; a nanoscale insoluble zirconium oxide compound; and an organic solvent.

[0048] The polymer for carbon hard masks according to an example of the present invention may include polycyclic aromatic compounds represented by the following chemical formula 1 or chemical formula 2.

[0049] Chemical Formula 1:

[0050] Chemical formula 2:

[0051] R1 can be independently selected from hydrogen, hydroxyl, C1-C10 alkyl, C6-C10 aryl, C3-C10 allyl, and halogen atoms; R3 can be independently selected from hydrogen, hydroxyl, and -C p H 2p In O, p is an integer from 1 to 7. R2 can be any compound group represented by the following chemical formulas (1-1) to (1-5), where n and m are repeating units, each being an independent integer from 1 to 100.

[0052] Chemical formula 1-1:

[0053] Chemical formulas 1-2:

[0054] Chemical formulas 1-3:

[0055] Chemical formulas 1-4:

[0056] Chemical formulas 1-5:

[0057] In the polymer represented by the chemical formula 1, when n is 2 or more, R1 and R2 contained in the monomer represented by the chemical formula 1 may be the same as or different from each other independently.

[0058] The polymer represented by the chemical formula 1 is prepared by polymerization of hydroxypyrene monomers substituted or unsubstituted with R1 and aldehyde monomers with compound groups introduced with R2.

[0059] In the polymer represented by the chemical formula 2, when m is 2 or more, R2 and R3 contained in the monomer represented by the chemical formula 2 may be independently the same as or different from each other.

[0060] The polymer represented by the chemical formula 2 is prepared by polymerization of fluorene monomers substituted or unsubstituted with R3 and aldehyde monomers with compound groups introduced with R2.

[0061] According to a preferred embodiment of the present invention, preferably, in the carbon hard mask polymers represented by chemical formula 1 or chemical formula 2 respectively, the plurality of R2 must contain compound groups represented by chemical formulas 1-5. The compound groups represented by chemical formulas 1-5 are compound groups derived from benzaldehyde, because the carbon hard mask polymers of the present invention, prepared using benzaldehyde as a monomer, have the advantage of achieving excellent planarization and gap-fill properties. To enable the carbon hard mask polymer to exhibit effective properties as a hard mask in semiconductor processes, a high-density network polymer with a high carbon content of 80-90% is preferred. The carbon hard mask polymer of the present invention is both a thermosetting resin and a polycyclic aromatic compound.

[0062] The polycyclic aromatic compounds of the hydroxypyrene series represented by the chemical formula 1 have a high carbon content, which can improve chemical resistance, maintain the surface properties of the film after thermal curing, and reduce the etching rate. Therefore, they have the advantage of giving the coating film hard properties.

[0063] The carbon content of the polycyclic aromatic compounds in the fluorene series represented by chemical formula 2 is relatively lower than that of the polycyclic aromatic compounds represented by chemical formula 1, but it can improve solubility and coatability. It has the advantages of controlling the formation of cracks in the film that may occur after thermal curing, poor coating of silicon nitride film, silicon oxide film and other deposited film on the wafer surface, uneven flatness characteristics, poor edge bead removal (EBR) and other problems.

[0064] Therefore, considering the respective properties of the polymer represented by Chemical Formula 1 and the polymer represented by Chemical Formula 2, the selection can be made according to the requirements of the applied semiconductor process.

[0065] The final polycyclic aromatic compound represented by Formula 1 or Formula 2 can be polymerized using a pyrene or fluorene-based monomer containing hydroxyl groups as the main monomer and an aldehyde compound such as terephthalaldehyde as a submonomer, which acts as a bridge between polymers. The resulting precipitate is then filtered, washed, and vacuum dried to obtain the polymer. The aldehyde compound, as a submonomer, can improve the curing degree of the polymer composition for carbon masks, and therefore, the properties required for the applied semiconductor process can be obtained by adjusting the content of the main monomer and submonomer.

[0066] The present invention is characterized by the fact that, unlike existing technologies, it can polymerize the polycyclic aromatic compounds described above without a thermal acid generator (TAG). Conventionally used thermal acid generators produce fume at temperatures of approximately 400°C, resulting in reduced stability during high-temperature baking processes and the release of outgassing. To overcome these drawbacks, the present invention derives polymers polymerized from compounds represented by Formula 1 or Formula 2, enabling the polymerization of polycyclic aromatic compounds without a thermal acid generator.

[0067] The carbon hard mask composition of the present invention is a self-crosslinking type composition that does not contain a curing agent.

[0068] According to one embodiment of the present invention, the weight-average molecular weight of the polymer used for the carbon hard mask is the weight-average molecular weight converted to polystyrene when determined by gel permeation chromatography (GPC), for example, it can be 2000 to 5000, or for example, 3000 to 4000. If the weight-average molecular weight of the polymer used for the carbon mask is less than 2000, it leads to a decrease in resistance during dry etching. On the other hand, if the weight-average molecular weight is greater than 5000, the increased viscosity may result in uneven coating or decreased dispersibility when coated with a spin coater.

[0069] A carbon hard mask composition according to an embodiment of the present invention comprises a polymer represented by chemical formula 1 or chemical formula 2 and an organic solvent. When the content of the organic solvent is 100 parts by weight, the content of the polymer represented by chemical formula 1 or chemical formula 2 is from 0.1 parts by weight to 40 parts by weight. If the content of the polymer for the carbon hard mask is less than 0.1 parts by weight, the insufficient carbon content in the composition may result in insufficient absorption of reflected light during exposure, and a decrease in the etch selectivity for the anti-reflective film and other etched layers during etching. Conversely, if the content of the polymer for the carbon hard mask is greater than 40 parts by weight, the increased viscosity of the composition may result in the inability to form a smooth carbon hard mask layer when coated by spin coating.

[0070] According to an embodiment of the present invention, preferably, the organic solvent is adjusted according to the amount of polymer added for the carbon hard mask. Examples of the organic solvent may include, but are not limited to, one or more of tetrahydronaphthalene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, propylene glycol n-propyl ether, dimethylformamide, γ-butyrolactone, ethoxyethanol, methoxyethanol, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate.

[0071] The insoluble zirconium oxide compound acts as a dispersant that facilitates easy mixing with the polymer used in the carbon hard mask. Zirconium oxide (ZiO2) is a metal oxide that is a compound of zirconium and oxygen, characterized by its chemical stability and high strength. Since zirconium oxide is hydrophilic, it is preferable to hydrophobize it to ensure uniform mixing with the organic polymer used in the carbon hard mask.

[0072] To hydrophobize zirconium oxide, silane coupling agents can be used. Silane coupling agents are substances used to mix organic and inorganic materials, allowing two different functional groups to be attached to silicon.

[0073] One of the two functional groups is a hydrolyzable group, which can be a halogen group, alkoxy group, acetoxy group, isopropenoxy group, silazane group, etc. Preferably, a silane coupling agent containing an alkoxy group with 1 to 5 carbon atoms is used. For example, trimethoxy (-(O-CH3)3) and triethoxy (-(O-CH2CH3)3) can be mainly used.

[0074] The remaining functional group is reactive with organic matter and can be selected from alkyl, epoxy, vinyl, acryloyloxy, amino, isocyanate, etc. Preferably, it can contain a straight-chain alkyl group with 1 to 5 carbon atoms.

[0075] According to a preferred embodiment of the present invention, the silane coupling agent may be selected from alkyltrimethoxysilane and alkyltriethoxysilane represented by the following chemical formula 3.

[0076] Chemical formula 3: Si(X)3(Y) In the chemical formula 3, X is a methoxy or ethoxy group, and Y is a C1-C7 straight-chain alkyl group.

[0077] If the alkyl group of the alkylalkoxysilane has more than 7 carbon atoms, the dispersibility may decrease due to the zirconium oxide particles becoming very bulky, and the etching resistance may decrease when used as a hard mask. Therefore, the number of carbon atoms in the alkyl group is preferably 1 to 7.

[0078] In this invention, when an alkyltrimethoxysilane or alkyltriethoxysilane represented by the chemical formula 3 is used as a silane coupling agent, the alkyl group may exist in the form of a mixture of one or more methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl groups.

[0079] When the hydrolyzable groups of the silane coupling agent are hydrolyzed by moisture in the air, silanol groups (Si-OH) are generated, and partially condense into oligomers. If the silanol and oligomers are adsorbed onto the surface of an inorganic material via hydrogen bonding, and the inorganic material is dried after adsorption, strong chemical bonds are formed with the inorganic material through a dehydration condensation reaction. Finally, if zirconium oxide is silanized using a silane coupling agent according to the process described above, a hydrophobic insoluble zirconium oxide compound can be obtained. Preferably, the insoluble zirconium oxide compound is obtained by silanizing zirconium oxide with an alkyltrimethoxysilane or an alkyltriethoxysilane as described above.

[0080] As described above, the insoluble zirconium oxide compound silanized with a silane coupling agent exhibits high dispersibility when mixed with the polymer for carbon hard masks of the present invention, thus improving the transparency of the resin composition even without using a dispersant alone. Furthermore, since no dispersant is included, there is no possibility of fume formation due to the use of a dispersant. Moreover, the combination of the organic polymer for carbon hard masks with the inorganic zirconium oxide compound improves the durability of the high-transparency resin composition, including chemical resistance and heat resistance.

[0081] According to one embodiment of the present invention, when the high-transparency resin composition for the hard mask is 100% by weight, the content of the insoluble zirconium oxide compound can be from 0.1% by weight to 40% by weight. If it is less than 0.1% by weight, the dispersion of inorganic matter in the high-transparency resin composition is weak; if it is greater than 40% by weight, there is a problem of decreased stability and toughness during etching.

[0082] The insoluble zirconium oxide compound of the present invention has a nanoscale size, specifically, an average diameter of 1 nm to 50 nm, for example, 5 nm to 20 nm, for example, 8 nm to 10 nm, preferably less than 10 nm. When the average particle size of the zirconium oxide compound is within the range described above, it has the advantage of significantly increased etching resistance.

[0083] The composition is characterized by being self-crosslinking without the use of curing agents or hot acid generators. Since the insoluble zirconium oxide compound is well dispersed and easily mixed in the polymer used for carbon hard masks, additives such as curing agents or hot acid generators are not required.

[0084] According to another embodiment of the present invention, a carbon hard mask can be formed by preparing a composition comprising a polymer represented by Chemical Formula 1 or Chemical Formula 2, a nanoscale insoluble zirconium oxide compound, and an organic solvent, coating it onto one side of a semiconductor device substrate, and then baking and crosslinking it. The details regarding the carbon hard mask composition are as described above. The carbon hard mask composition is in a state where the carbon hard mask polymer is dispersed in the organic solvent, and can be spin-coated onto the substrate to a thickness of 100 to 300 nm. The spin-coating can be performed using a spin coater commonly used in semiconductor processes. Compared to existing methods of deposition using vacuum chemical deposition (CVD), spin-coating has the advantages of reducing defects such as clusters formed by chemical vapor aggregation, and the carbon hard mask layer is formed uniformly and smoothly after baking. The carbon hard mask composition coated on the substrate is baked at a temperature of 200°C to 300°C for 45 to 90 seconds.

[0085] The baking can be performed in a hot air oven or on a hot plate, but it is preferred to perform it on a hot plate to ensure the homogeneity of the carbon hard mask layer. In this case, the organic solvent evaporates, and the polymer used for the carbon hard mask undergoes cross-linking.

[0086] Before coating the carbon hard mask composition, a metal layer can be formed on the substrate. The metal layer may comprise metals such as aluminum, gold, or copper. The metal layer can be formed using methods already employed in semiconductor processes, such as sputtering, evaporation, or electroplating. Even after further forming a metal layer on the substrate, the carbon hard mask composition can be coated using the same method described above.

[0087] Then, an anti-reflective film and a photoresist layer are formed on the carbon hard mask. The photoresist layer is exposed and developed, and the carbon hard mask is etched to form a pattern. The anti-reflective film and the photoresist layer can be anti-reflective films and photoresist layers used in semiconductor processes. Furthermore, the process of exposing and developing the photoresist can also be performed using processes commonly used in existing semiconductor processes. Using the pattern of the photoresist, the carbon hard mask layer is etched a first time using a CHF3 / CF4 mixed gas, and then a second time using O2 gas. This two-step etching is performed to remove the SiON layer and the carbon hard mask. Detailed Implementation

[0088] The present invention will now be described in more detail through embodiments. However, the following embodiments are merely examples of the present invention, and the scope of the present invention is not limited to the following embodiments.

[0089] Synthesis example Synthesis example 1 200g of propylene glycol monomethyl ether acetate (PGMEA) was placed in a 1L flask equipped with a stirrer and thermometer. 35.0g of 1-hydroxypyrene was added, and the mixture was stirred until dissolved, while the internal temperature was heated to 140°C. 23.0g of terephthalaldehyde and 3.05g of benzaldehyde were slowly added dropwise using a dropping funnel over 1 hour, followed by stirring for 5 hours.

[0090] To terminate the reaction, 4.48 g of triethanolamine was dissolved in 20 g of PGMEA and added dropwise to the reaction solution. The mixture was stirred and slowly cooled to room temperature in the dark. The resulting solution was then added to 3 L of hexane. The precipitate was filtered, washed, and vacuum dried to obtain the polymer. The polymer obtained at this point had a weight-average molecular weight of 3800 (based on GPC conversion of polystyrene).

[0091] Synthesis example 2 200g of propylene glycol monomethyl ether acetate (PGMEA) was placed in a 1L flask equipped with a stirrer and thermometer. 35g of 9,9-bis(3,5-diphenyl-4-hydroxyphenyl)fluorene was added and dissolved while stirring, and the internal temperature was heated to 190°C. A mixture of 23.0g of terephthalaldehyde and 3.05g of benzaldehyde was slowly added dropwise over a dropping funnel for 1 hour, followed by stirring for 9 hours.

[0092] The resulting solution was then added to 3 L of hexane, and the resulting precipitate was filtered, washed, and vacuum dried to obtain the polymer. The polymer obtained at this point had a GPC-converted weight-average molecular weight of 3500 for polystyrene.

[0093] Example Example 1 The polymer prepared in Synthesis Example 1 was mixed with an insoluble zirconium oxide compound (Pixelligent, PCPR-50-PGA, ZNP 1) with an average diameter of 5 nm at a weight ratio of 60:40. Then, the mixture was mixed with propylene glycol monomethyl ether acetate (PGMEA) at a weight ratio of 18.3:81.7 to prepare 100 g of resin composition.

[0094] Example 2 The polymer prepared in Synthesis Example 1 and the insoluble zirconium oxide compound (ZNP 2) were mixed at a weight ratio of 60:40. Then, the mixture was mixed with propylene glycol monomethyl ether acetate (PGMEA) at a weight ratio of 18.3:81.7 to obtain 100 g of resin composition.

[0095] The “ZNP 2” is obtained by surface treatment of the “ZNP 1” particles with a silane coupling agent represented by the following chemical formula 3-1.

[0096] Chemical formula 3-1: (r is an integer from 1 to 5) Example 3 The polymer prepared in Synthesis Example 1 and the insoluble zirconium oxide compound (ZNP 3) were mixed at a weight ratio of 60:40. Then, the mixture was mixed with propylene glycol monomethyl ether acetate (PGMEA) at a weight ratio of 18.3:81.7 to prepare a resin composition.

[0097] The “ZNP 3” is obtained by surface treatment of the “ZNP 1” particles with a silane coupling agent represented by the following chemical formula 3-2.

[0098] Chemical formula 3-2: (s is an integer from 1 to 5) Comparative Example 1 The polymer prepared in Synthesis Example 1 and propylene glycol monomethyl ether acetate (PGMEA) were mixed at a weight ratio of 14.58:85.42 to prepare 100g of resin composition.

[0099] Example 4 The polymer prepared in Synthesis Example 2 and the insoluble zirconium oxide compound (Pixelligent, PCPR-50-PGA, ZNP 1) were mixed at a weight ratio of 60:40. Then, the mixture was mixed with propylene glycol monomethyl ether acetate (PGMEA) at a weight ratio of 17.20:82.80 to prepare 100 g of resin composition.

[0100] Example 5 To prepare the polymer prepared in Synthesis Example 2, the polymer and the insoluble zirconium oxide compound (ZNP 2) used in Example 2 were mixed at a weight ratio of 60:40. Then, the mixture was mixed with propylene glycol monomethyl ether acetate (PGMEA) at a weight ratio of 16.88:83.12 to prepare 100 g of resin composition.

[0101] Example 6 To prepare the polymer prepared in Synthesis Example 2, the polymer and the insoluble zirconium oxide compound (ZNP 3) used in Example 3 were mixed at a weight ratio of 60:40. Then, the mixture was mixed with propylene glycol monomethyl ether acetate (PGMEA) at a weight ratio of 16.91:83.09 to prepare 100 g of resin composition.

[0102] Comparative Example 2 The polymer prepared in Synthesis Example 2 and propylene glycol monomethyl ether acetate (PGMEA) were mixed in a weight ratio of 13.76:86.24 to prepare a resin composition.

[0103] Experimental Example 1. Haze Measurement - Transparency Evaluation The transparency of the compositions prepared in the examples and comparative examples was evaluated by measuring the haze in solution. Specifically, the haze was measured using a diffusion characteristics analysis system (Nippon Denshoku, NDH-5000) at 23°C. A haze value of "0" indicates excellent transparency (◎). If haze is present, the resin composition will become turbid and precipitate, and the process stability will decrease; therefore, a haze value of 0 is required.

[0104] 2. Determine the etching rate. The Nanotechnology Institute (NNFC) was commissioned to evaluate CF4 gas and O2N2 gas etching and to determine the etching rate (E / R). In this case, the thickness was 4000 Å. The equipment used for the measurement was the LAM TCP-9400 DFM.

[0105] When evaluating etching resistance, Examples 1 to 3 were compared with Comparative Example 1, and Examples 4 to 6 were compared with Comparative Example 2.

[0106] 3. Coating performance evaluation Using the DNS VM-3500 equipment, the coated wafer was placed on the equipment, and the thickness from the surface to the wafer was measured. If the total thickness met the standard of 4000ű40Å, it was evaluated as having excellent coating properties (◎).

[0107] The results of the experiments conducted using the resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 2 are shown in Table 1 below.

[0108] Table 1

[0109] As shown in Table 1, it can be confirmed that Examples 1 to 6 of the present invention all achieve excellent coating properties and transparency, and the etching resistance is also significantly improved compared with Comparative Examples 1 and 2.

[0110] The present invention has been described in more detail above with reference to embodiments of this specification. However, this specification is not necessarily limited to these embodiments, and various modifications can be made without departing from the technical spirit of this specification. Therefore, the embodiments disclosed in this specification are not intended to limit the technical spirit of this specification, but are intended to illustrate that the scope of the technical spirit of this specification is not limited to these embodiments. Therefore, the above embodiments should be understood as exemplary in all respects and not restrictive. The scope of protection of the invention as claimed in this specification should be interpreted by the claims, and all technical ideas within the equivalent scope should be interpreted as being included within the scope of protection of the invention as claimed in this specification.

Claims

1. A highly transparent resin composition for use in hard masks, characterized in that, Include: Polymers for carbon hard masks; Insoluble zirconium oxide compounds with an average diameter of 1 nm to 50 nm; and Organic solvents.

2. The high-transparency resin composition for hard masks according to claim 1, characterized in that, The polymer used for the carbon hard mask includes polymers represented by the following chemical formula 1 or chemical formula 2: Chemical Formula 1: Chemical formula 2: In Formula 1, R1 atoms may be the same or different from each other, and are independently selected from hydrogen, hydroxyl, C1-C10 alkyl, C6-C10 aryl, C3-C10 allyl, and halogen atoms. In chemical formula 2, the R3 groups may be the same or different from each other, and each group is independently selected from hydrogen, hydroxyl, and -C. p H 2p In O, p is an integer from 1 to 7. The R2 groups of chemical formula 1 and / or chemical formula 2 may be the same or different from each other, and each independently represents any one of the compound groups represented by chemical formulas (1-1) to (1-5) below. n and m are repeating units, each being an independent integer from 1 to 100. Chemical formula 1-1: , Chemical formulas 1-2: , Chemical formulas 1-3: , Chemical formulas 1-4: , Chemical formulas 1-5: .

3. The high-transparency resin composition for hard masks according to claim 2, characterized in that, In the chemical formula 1, one or more of R2 contains a compound group represented by chemical formulas 1-5.

4. The high-transparency resin composition for hard masks according to claim 2, characterized in that, In the chemical formula 2, one or more of R2 contains compound groups represented by chemical formulas 1-5.

5. The high-transparency resin composition for hard masks according to claim 1, characterized in that, The weight-average molecular weight of the polymer used for the carbon hard mask is between 2000 and 5000.

6. The high-transparency resin composition for hard masks according to claim 1, characterized in that, The insoluble zirconium oxide compound is a compound obtained by surface treatment of zirconium oxide with a hydrophobic surface treatment agent.

7. The high-transparency resin composition for hard masks according to claim 6, characterized in that, The hydrophobic surface treatment agent is a silane coupling agent containing alkoxy groups.

8. The high-transparency resin composition for hard masks according to claim 7, characterized in that, The silane coupling agent is selected from alkyltrimethoxysilanes and alkyltriethoxysilanes represented by the following chemical formula 3: Chemical formula 3: Si(X)3(Y) In the chemical formula 3, X is a methoxy or ethoxy group, and Y is a C1-C7 straight-chain alkyl group.

9. The high-transparency resin composition for hard masks according to claim 1, characterized in that, When the high-transparency resin composition for hard masks is 100% by weight, the content of the insoluble zirconium oxide compound is from 0.1% to 40% by weight.

10. The high-transparency resin composition for hard masks according to claim 1, characterized in that, The organic solvent includes one or more of tetrahydronaphthalene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, propylene glycol n-propyl ether, dimethylformamide, γ-butyrolactone, ethoxyethanol, methoxyethanol, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate.

11. A method for forming a pattern in a semiconductor device, characterized in that, Use the high-transparency resin composition for hard masks according to any one of claims 1 to 10.

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