Highly transparent resin composition comprising insoluble zirconia compound and carbon hard mask polymer

Abstract

The present invention relates to a highly transparent resin composition which can be utilized in a semiconductor etching process and, more specifically, to a highly transparent resin composition comprising an insoluble zirconia compound and a carbon hard mask polymer, which can suppress the occurrence of fumes while improving coatability, transparency, and etching performance in a semiconductor etching process.

Description

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

[0001] The present invention relates to a highly transparent resin composition that can be utilized in a semiconductor etching process, and more particularly, to a highly transparent resin composition comprising an insoluble zirconia compound and a carbon hard mask polymer that can improve coating properties, transparency, and etching performance in a semiconductor etching process while suppressing fume generation.

[0002] In the lithography process of semiconductor manufacturing, a hard mask layer is formed between the material layer to be etched and the photoresist layer to effectively etch fine patterns. The hard mask acts as an intermediate layer that transfers the photoresist pattern to the material layer.

[0003] The hard mask material applied to the existing lithography process is either the organic polymer resin itself or an amorphous carbon layer (ACL). Since the use of the organic polymer resin itself is preferred over the process of depositing the amorphous carbon layer (ACL) in terms of process efficiency, organic hard masks using organic polymer resins have been used recently. On the other hand, although there are many types of conventional organic hard mask materials, the etch performance level at the same thickness is low compared to the amorphous carbon layer (ACL) which was mainly used on the substrate. Therefore, a process with a higher thickness than the amorphous carbon layer (ACL) is required to achieve the desired etch performance.

[0004] In order to create a high-thickness circuit pattern when forming a pattern for manufacturing a recently highly integrated semiconductor material, the thickness of the organic hard mask material with low etching performance becomes thicker, and as the aspect ratio of the height and bottom according to the thickness increases, there is a problem that the pattern collapses or the resist profile does not maintain an ideal shape, resulting in a phenomenon in which the etch bias varies greatly.

[0005] To this end, hardmask compositions have been manufactured and evaluated using various inorganic materials (e.g., silica, carbon nanotubes (CNTs), zirconia, etc.) in addition to conventional organic polymers. However, when using inorganic materials, a dispersant must be separately added to ensure even dispersion within the hardmask material. In addition, when coating using only inorganic materials, it is difficult to maintain a uniform thickness as the thickness increases beyond 3000 Å. In addition, when using only inorganic materials, the transparency decreases (haze increases) as the thickness increases, making it difficult to align with the underlying film, which makes subsequent processes difficult. In addition, the application of dispersants and the use of thermally oxidizing agents (TAGs) used to increase the coating property and to evenly apply them to the substrate present problems in that they generate fumes and outgases that cause equipment contamination in situations where conventional high-temperature processes of 300°C or higher are applied. Therefore, technological development to solve these problems is necessary.

[0006] The present invention aims to provide a highly transparent resin composition that can easily mix with a polymer for a carbon hard mask without a dispersant by using an insoluble zirconia compound, thereby solving the problem of fume and outgas generation due to a dispersant and a thermal acid generator, and improving the durability, transparency, and etching characteristics of the hard mask.

[0007] The purpose of the present invention is not limited to the aforementioned purposes, and other unmentioned purposes and advantages of the present invention can be understood through the following description and will be more clearly understood through the embodiments of the present invention. Furthermore, it will be readily apparent that the purposes and advantages of the present invention can be realized by the means and combinations thereof set forth in the claims.

[0008] In order to achieve the above object, according to one aspect of the present invention, a highly transparent resin composition for a hard mask is provided, comprising: a polymer for a carbon hard mask; a nano-sized insoluble zirconia compound having an average diameter of 1 nm to 50 nm; and an organic solvent.

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

[0010] [Chemical Formula 1]

[0011] [Chemical Formula 2]

[0012] R1 in chemical formula 1 is the same or different from each other, and is independently selected from hydrogen, a hydroxyl group, a C1-C10 alkyl group, a C6-C10 aryl group, a C3-C10 allyl group, and a halogen atom,

[0013] R3 in chemical formula 2 are the same or different, and each independently represents hydrogen, a hydroxyl group, and -C p H 2p O is selected, and p is an integer from 1 to 7,

[0014] R2 of Chemical Formula 1 and / or Chemical Formula 2 is the same as or different from each other, and is any one of the chemical compounds represented by Chemical Formula (1-1) to Chemical Formula (1-5) below,

[0015] n and m are each independently integers from 1 to 100 as repeating units.

[0016] [Chemical Formula 1-1]

[0017] [Chemical Formula 1-2]

[0018] [Chemical Formula 1-3]

[0019] [Chemical Formula 1-4]

[0020] [Chemical Formula 1-5]

[0021] In the above chemical formula 1, at least one of R2 includes a compound group represented by chemical formula 1-5.

[0022] In the above chemical formula 2, at least one of R2 includes a compound group represented by chemical formula 1-5.

[0023] The weight average molecular weight of the polymer for the above carbon hard mask may be 2,000 to 5,000.

[0024] The above insoluble zirconia compound may be zirconia surface-treated with a hydrophobic surface treatment agent.

[0025] The above hydrophobic surface treatment agent may be a silane coupling agent containing an alkoxy group.

[0026] The above silane coupling agent may be selected from alkyltrimethoxysilane and alkyltriethoxysilane represented by the following chemical formula 3.

[0027] [Chemical Formula 3] Si(X)3(Y)

[0028] In the above chemical formula 3, X is a methoxy group or an ethoxy group, and Y is a C1-C7 straight-chain alkyl group.

[0029] When the high-transparency resin composition for the hard mask is 100 wt%, the insoluble zirconia compound may be included in an amount of 0.1 wt% to 40 wt%.

[0030] 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, dimethyl formamide, gamma-butyrolactone, ethoxyethanol, methoxyethanol, methyl-3-methoxypropionate, and ethyl-3-ethoxypropionate.

[0031] According to another aspect of the present invention, a method for forming a pattern of a semiconductor device using a high-transparency resin composition for a hard mask according to one aspect of the present invention can be provided.

[0032] The weight average molecular weight of the polymer for the above carbon hard mask may be 2,000 to 5,000.

[0033] The above insoluble zirconia compound may be zirconia surface-treated with a hydrophobic surface treatment agent.

[0034] The above hydrophobic surface treatment agent may be a silane coupling agent containing an alkoxy group.

[0035] The above silane coupling agent may be selected from alkyltrimethoxysilane and alkyltriethoxysilane represented by the following chemical formula 3.

[0036] [Chemical Formula 3] Si(X)3(Y)

[0037] In the above chemical formula 3, X is a methoxy group or an ethoxy group, and Y is a C1-C7 straight-chain alkyl group.

[0038] When the high-transparency resin composition for the hard mask is 100 wt%, the insoluble zirconia compound may be included in an amount of 0.1 wt% to 40 wt%.

[0039] 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, dimethyl formamide, gamma-butyrolactone, ethoxyethanol, methoxyethanol, methyl-3-methoxypropionate, and ethyl-3-ethoxypropionate.

[0040] According to another aspect of the present invention, a method for forming a pattern of a semiconductor device using a high-transparency resin composition for a hard mask according to one aspect of the present invention can be provided.

[0041] According to the high transparency resin composition according to the present invention, an insoluble zirconia compound can be easily mixed with a polymer for a carbon hard mask without a dispersant.

[0042] According to the high transparency resin composition of the present invention, since it does not contain a dispersant and a thermal oxidation agent, it is possible to prevent equipment contamination by eliminating the decrease in coating properties, decrease in transparency, fume, and outgas caused by the dispersant, and to improve process efficiency through shortening process time and reducing repair costs.

[0043] The high transparency resin composition according to the present invention enables 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.

[0044] The highly transparent resin composition according to the present invention can exhibit excellent flattening properties and gap-fill properties.

[0045] The effects of the present invention are not limited to those mentioned above, and other effects not mentioned will be readily apparent to those skilled in the art from the description of the claims. In addition to the effects described above, the effects of the present invention are further described below along with the description of the steps involved in implementing the invention.

[0046] The aforementioned purposes, features, and advantages are described in detail below with reference to the present specification, thereby enabling those skilled in the art to readily implement the technical concepts of the present invention. In describing the present invention, detailed descriptions of known technologies related to the present invention will be omitted if they are deemed to unnecessarily obscure the gist of the invention.

[0047] In describing this specification, if it is determined that a detailed description of a related known technology may unnecessarily obscure the gist of this specification, the detailed description is omitted.

[0048] In this specification, when the terms "includes," "has," "contains," "arranges," and "provides" are used for a component, other parts may be added, unless "only" is used. When a component is expressed in the singular, it includes the plural unless otherwise explicitly stated.

[0049] When it is said in this specification that an element is positioned "on" another element, this includes not only cases where the element is in contact with the other element, but also cases where another element exists between the elements.

[0050] In this specification, the mean diameter of nano-sized particles is the average diameter of nanocrystals measured by dynamic light scattering (DLS).

[0051] Hereinafter, the present invention will be described in more detail.

[0052] According to one aspect of the present invention, a highly transparent resin composition for a hard mask can be provided, comprising: a polymer for a carbon hard mask; a nano-sized insoluble zirconia compound; and an organic solvent.

[0053] A polymer for a carbon hard mask according to one embodiment of the present invention may include a polycyclic aromatic compound represented by the following chemical formula 1 or chemical formula 2.

[0054] [Chemical Formula 1]

[0055] [Chemical Formula 2]

[0056] R1 can be independently selected from hydrogen, a hydroxyl group, a C1-C10 alkyl group, a C6-C10 aryl group, a C3-C10 allyl group and a halogen atom, and R3 can be independently selected from hydrogen, a hydroxyl group and -C p H 2p O can be selected from,

[0057] p is an integer from 1 to 7,

[0058] R2 may be any one of the compound groups represented by the following chemical formulas (1-1) to (1-5), and n and m are each independently an integer from 1 to 100 as a repeating unit.

[0059] [Chemical Formula 1-1]

[0060] [Chemical Formula 1-2]

[0061] [Chemical Formula 1-3]

[0062] [Chemical Formula 1-4]

[0063] [Chemical Formula 1-5]

[0064] In the polymer represented by the above chemical formula 1, when n is 2 or more, R1 and R2 included in the monomer represented by the chemical formula 1 may each independently be the same as or different from each other.

[0065] The polymer represented by the above chemical formula 1 is prepared by polymerization of a hydroxypyrene monomer substituted or unsubstituted with R1 and an aldehyde monomer introducing a compound group of R2.

[0066] When m is 2 or more in the polymer represented by the above chemical formula 2, R2 and R3 included in the monomer represented by the chemical formula 2 may each independently be the same as or different from each other.

[0067] The polymer represented by the above chemical formula 2 is prepared by polymerization of a fluorene monomer substituted or unsubstituted with R3 and an aldehyde monomer introducing a compound group of R2.

[0068] According to a preferred embodiment of the present invention, it is preferable that each of the polymers for carbon hard masks represented by the above chemical formula 1 or 2 necessarily include a compound group represented by the above chemical formula 1-5 among a plurality of R2. The compound group represented by the above chemical formula 1-5 is a compound group derived from benzaldehyde, and the polymer for carbon hard masks of the present invention manufactured by including benzaldehyde as a monomer has the advantage of being able to implement excellent planarization characteristics and gap-fill characteristics. In order for the polymer for carbon hard masks to exhibit effective characteristics as a hard mask in a semiconductor process, it is preferable that it be a high-density networking polymer containing a high content of carbon of 80 to 90% in the molecule, and therefore, the polymer for carbon hard masks according to the present invention is a thermosetting resin and a polycyclic aromatic compound.

[0069] The polycyclic aromatic compound of the hydroxypyrene series represented by the above chemical formula 1 has a high carbon content, which can increase chemical resistance, and is an aromatic compound of the type that can maintain the surface properties of the film without collapsing after heat curing and can lower the etching rate, and has the advantage of providing a hard characteristic to the coating film.

[0070] The fluorene series polycyclic aromatic compound represented by the above chemical formula 2 has a relatively low carbon content compared to the polycyclic aromatic compound represented by the chemical formula 1, but can increase solubility and coatability, and has an advantage in controlling problematic phenomena such as cracks in the film quality that may occur after thermal curing, poor coating on the wafer surface for deposited film quality such as silicon nitride film and silicon oxide film, uneven flatness characteristics, and poor EBR (Edge Bead Removal).

[0071] Therefore, considering the characteristics of each of the polymers represented by the above chemical formula 1 and the polymers represented by the chemical formula 2, they can be selected according to the needs of the applied semiconductor process.

[0072] The polycyclic aromatic compound represented by the final chemical formula 1 or 2 is a sub-monomer that acts as a bridge between the main monomer and the polymer containing a hydroxyl group, such as a pyrene-based or fluorene-based polymer, and an aldehyde compound such as terephthalaldehyde is polymerized, and the resulting precipitate is then filtered through a membrane filter, washed, and vacuum-dried to obtain a polymer. Since the aldehyde compound as the sub-monomer can increase the degree of curing of the polymer composition for a carbon mask, the composition can be provided with the required characteristics according to the applied semiconductor process by controlling the contents of the main monomer and the sub-monomer.

[0073] The present invention is characterized in that, unlike the prior art, when polymerizing the above-mentioned polyaromatic compound, polymerization is performed without a thermal acid generator (TAG). Conventionally, thermal acid generators commonly used generate fumes at a temperature of about 400°C, and thus have the disadvantages of low stability and emitting outgas during a high-temperature baking process. In order to complement these disadvantages, the present invention has derived a polymer polymerized with a compound represented by Chemical Formula 1 or a polymer polymerized with a compound represented by Chemical Formula 2 so as to polymerize a polycyclic aromatic compound without a thermal acid generator.

[0074] The composition for a carbon hard mask according to the present invention is a self-crosslinking composition that does not contain a curing agent.

[0075] According to one embodiment of the present invention, the weight average molecular weight of the polymer for the carbon hard mask may be, as measured by gel permeation chromatography (GPC), a polystyrene-converted weight average molecular weight, for example, 2,000 to 5,000, for example, 3,000 to 4,000. If the weight average molecular weight of the polymer for the carbon mask is less than 2,000, the resistance to dry etching decreases. On the other hand, if the weight average molecular weight exceeds 5,000, the viscosity increases, so that the polymer may not be evenly applied when applied with a spin coater, or the dispersibility may be reduced.

[0076] A composition for a carbon hard mask according to one embodiment of the present invention includes a polymer represented by Chemical Formula 1 or Chemical Formula 2 and an organic solvent. The polymer represented by Chemical Formula 1 or Chemical Formula 2 is included in an amount of 0.1 to 40 parts by weight based on 100 parts by weight of the organic solvent. If the polymer for a carbon hard mask is included in an amount of less than 0.1 parts by weight, the carbon content in the composition for a carbon hard mask is insufficient, so that reflected light cannot be easily absorbed during exposure, and the etching selectivity for an anti-reflection film and other layers to be etched decreases during etching. On the other hand, if the polymer for a carbon hard mask is included in an amount exceeding 40 parts by weight, the viscosity of the composition increases, so that a carbon hard mask layer may not be formed flat when applied by spin coating.

[0077] According to one embodiment of the present invention, it is preferable to adjust the organic solvent according to the amount of the polymer for the carbon hard mask added. 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, dimethyl formamide, gamma-butyrolactone, ethoxyethanol, methoxyethanol, methyl-3-methoxypropionate, and ethyl-3-ethoxypropionate.

[0078] The above-mentioned insoluble zirconia compound acts as a dispersant to facilitate mixing with the polymer for the carbon hard mask. Zirconia (zirconium dioxide, ZiO2, zirconia) is a metal oxide compound of zirconium and oxygen, and is characterized by chemical stability and high strength. Since zirconia is a hydrophilic material, it is desirable to hydrophobize it to ensure uniform mixing with the organic polymer for the carbon hard mask.

[0079] To hydrophobize zirconia, a silane coupling agent can be used. A silane coupling agent is a substance used to mix organic and inorganic materials, and two different functional groups can be attached to the silicon element.

[0080] One of the above two functional groups is a hydrolyzable group, and a halogen group, an alkoxy group, an acetoxy group, an isopropenoxy group, a silazane group, etc. can be selected, and preferably, a silane coupling agent containing an alkoxy group having 1 to 5 carbon atoms is used. For example, a trimethoxy group (-(O-CH3)3) and a triethoxy group (-(O-CH2CH3)3) can be mainly used.

[0081] The remaining functional group is reactive with organic matter, and may be selected from an alkyl group such as epoxy, vinyl, acryloxy, amino, or isocyanato, and preferably may contain a straight-chain alkyl group having 1 to 5 carbon atoms.

[0082] 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.

[0083] [Chemical Formula 3] Si(X)3(Y)

[0084] In the above chemical formula 3, X is a methoxy group or an ethoxy group, and Y is a C1-C7 straight-chain alkyl group.

[0085] If the number of carbon atoms in the alkyl group of the above alkylalkoxysilane exceeds 7, the zirconia particles become too bulky, which reduces dispersibility and may lead to a decrease in etching resistance when applied as a hard mask. Therefore, it is preferable that the number of carbon atoms in the alkyl group be 1 to 7.

[0086] In the present invention, when alkyltrimethoxysilane or alkyltriethoxysilane represented by the above chemical formula 3 is used as a silane coupling agent, the alkyl group may exist in a mixed form of one or more of a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group.

[0087] When the hydrolyzable group of the above silane coupling agent is hydrolyzed by moisture in the air, a silanol group (Si-OH) is generated, which partially condenses to form an oligomer state. The silanol and oligomer are adsorbed to the surface of an inorganic substance through hydrogen bonding, and when the inorganic substance is dried after adsorption, a strong chemical bond with the inorganic substance is formed through a dehydration condensation reaction. Consequently, when zirconia is silanized using a silane coupling agent according to the process described above, an insoluble zirconia compound having hydrophobicity can be obtained. The insoluble zirconia compound is preferably obtained by silanizing zirconia with the above-mentioned alkyltrimethoxysilane or alkyltriethoxysilane.

[0088] As such, the insoluble zirconia compound silanized with a silane coupling agent has high dispersibility when mixed with the polymer for carbon hard masks of the present invention, so that the transparency of the resin composition can be improved without the use of a separate dispersant. In addition, since no dispersant is included, there is no possibility of a fume phenomenon occurring due to the use of a dispersant. Furthermore, the combination of the organic carbon hard mask polymer and the insoluble zirconia compound, which is an inorganic substance, can improve the durability, such as the chemical resistance and heat resistance, of the highly transparent resin composition.

[0089] According to one embodiment of the present invention, when the high-transparency resin composition for the hard mask is 100 wt%, the insoluble zirconia compound may be included in an amount of 0.1 wt% to 40 wt%. If it is less than 0.1 wt%, the effect of dispersing the inorganic material within the high-transparency resin composition is minimal, and if it exceeds 40 wt%, there is a problem of reduced stability and resistance in etching.

[0090] The insoluble zirconia compound according to the present invention has a nano-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, and preferably 10 nm or less. When the average particle diameter of the zirconia compound is within the above range, there is an advantage in that etching resistance is drastically increased. There is an advantage in this respect.

[0091] The above composition is characterized by being a self-crosslinking type that does not use a hardener or thermal oxidizer. Since the insoluble zirconia compound is well dispersed and easily mixed within the polymer for carbon hard masks, additives such as a hardener or thermal oxidizer are not required.

[0092] According to another aspect of the present invention, a carbon hardmask composition comprising a polymer represented by the above chemical formula 1 or 2, a nano-sized insoluble zirconia compound, and an organic solvent is prepared, applied onto one surface of a semiconductor device substrate, baked, and crosslinked to form a carbon hardmask. The details of the carbon hardmask composition are the same as those described above. The carbon hardmask composition, in which the carbon hardmask polymer is dispersed in the organic solvent, can be applied to the substrate at a thickness of 100 to 300 nm by spin coating. The spin coating can be performed using a spin coater generally used in semiconductor processes. When applied by the spin coating method, defects such as clusters of chemical vapors can be reduced compared to a conventional vacuum state chemical vapor deposition (CVD) deposition method, and the carbon hardmask layer is advantageously formed uniformly and flatly after the baking. The composition for the carbon hard mask applied to the substrate is baked at 200°C to 300°C for 45 to 90 seconds.

[0093] The above baking can be performed in a hot air oven or a hot plate, and is preferably performed on a hot plate to ensure the homogeneity of the carbon hard mask layer. At this time, the organic solvent volatilizes and crosslinking of the polymer for the carbon hard mask occurs.

[0094] Before applying the composition for the carbon hard mask, a metal layer may be formed on the substrate. The metal layer may include a metal such as aluminum, gold, or copper. The method for forming the metal layer may use a method used in a conventional semiconductor process, such as sputtering, evaporation, or plating. Even if a metal layer is further formed on the substrate, the composition for the carbon hard mask may be applied using the same method as described above.

[0095] After this, an anti-reflection 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-reflection film and the photoresist layer may be an anti-reflection film and a photoresist layer used in a semiconductor process. In addition, the process of exposing and developing the photoresist may also be performed as a process generally used in a conventional semiconductor process. Using the pattern of the photoresist, the carbon hard mask layer is first etched using a CHF3 / CF4 mixed gas, and then second etched using O2 gas. The reason for performing the etching twice is to remove the SiON layer and the carbon hard mask.

[0096] Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited to the following examples.

[0097] [Synthesis example]

[0098] Synthesis Example 1

[0099] 200 g of propylene glycol monomethyl ether acetate (PGMEA) was placed in a 1 L flask equipped with a stirrer and thermometer, 35.0 g of 1-hydroxypyrene was added, and the mixture was stirred to dissolve while heating to an internal temperature of 140°C. 23.0 g of terephthalaldehyde and 3.05 g of benzaldehyde were slowly added dropwise over 1 hour using a dropping funnel, and then stirred for 5 hours.

[0100] To terminate the reaction, 4.48 g of triethanolamine was dissolved in 20 g of PGMEA, added dropwise, stirred, and slowly cooled to room temperature. The resulting solution was then added to 3 liters of hexane, and the resulting precipitate was filtered, washed, and vacuum-dried to obtain a polymer. The obtained polymer had a polystyrene-converted weight-average molecular weight of 3,800 using GPC.

[0101] Synthesis Example 2

[0102] 200 g of propylene glycol monomethyl ether acetate (PGMEA) was placed in a 1 L flask equipped with a stirrer and thermometer, 35 g of 9,9-bis(3,5-diphenyl-4-hydroxyphenyl)fluorene was added, and the mixture was heated to an internal temperature of 190°C while stirring to dissolve. Using a dropping funnel, 23.0 g of terephthalaldehyde and 3.05 g of benzaldehyde were slowly added dropwise over 1 hour, and the mixture was stirred for 9 hours.

[0103] The resulting solution was then added to 3 liters of hexane, and the resulting precipitate was filtered, washed, and vacuum-dried to obtain a polymer. The polymer thus obtained had a polystyrene-equivalent weight-average molecular weight of 3,500 using GPC.

[0104] [Example]

[0105] Example 1

[0106] The polymer manufactured in Synthesis Example 1 and an insoluble zirconia compound (Pixelligent, PCPR-50-PGA, ZNP 1) having an average diameter of 5 nm were mixed at a weight ratio of 60:40. Then, the mixture and propylene glycol monomethyl ether acetate (PGMEA) were mixed at a weight ratio of 18.3:81.7 to manufacture 100 g of a resin composition.

[0107] Example 2

[0108] The polymer and insoluble zirconia compound (ZNP 2) manufactured in Synthesis Example 1 were mixed at a weight ratio of 60:40. Then, the mixture and propylene glycol monomethyl ether acetate (PGMEA) were mixed at a weight ratio of 18.3:81.7 to manufacture 100 g of a resin composition.

[0109] The above 'ZNP 2' is a particle of the above 'ZNP 1' surface treated with a silane coupling agent represented by the following chemical formula 3-1.

[0110] [Chemical Formula 3-1] (r is an integer from 1 to 5)

[0111] Example 3

[0112] The polymer and insoluble zirconia compound (ZNP 3) manufactured in Synthesis Example 1 were mixed at a weight ratio of 60:40. Then, the mixture and propylene glycol monomethyl ether acetate (PGMEA) were mixed at a weight ratio of 18.3:81.7 to manufacture a resin composition.

[0113] The above 'ZNP 3' is a particle of the above 'ZNP 1' surface treated with a silane coupling agent represented by the following chemical formula 3-2.

[0114] [Chemical Formula 3-2] (s is an integer from 1 to 5)

[0115] Comparative Example 1

[0116] The polymer manufactured in Synthesis Example 1 and propylene glycol monomethyl ether acetate (PGMEA) were mixed in a weight ratio of 14.58:85.42 to manufacture 100 g of a resin composition.

[0117] Example 4

[0118] The polymer manufactured in Synthesis Example 2 and an insoluble zirconia compound (Pixelligent, PCPR-50-PGA, ZNP 1) were mixed at a weight ratio of 60:40. Then, the mixture and propylene glycol monomethyl ether acetate (PGMEA) were mixed at a weight ratio of 17.20:82.80 to manufacture 100 g of a resin composition.

[0119] Example 5

[0120] The polymer manufactured in Synthesis Example 2 was prepared, and the polymer and the insoluble zirconia compound (ZNP 2) used in Example 2 were mixed at a weight ratio of 60:40. Then, the mixture and propylene glycol monomethyl ether acetate (PGMEA) were mixed at a weight ratio of 16.88:83.12 to prepare 100 g of a resin composition.

[0121] Example 6

[0122] The polymer manufactured in Synthesis Example 2 was prepared, and the polymer and the insoluble zirconia compound (ZNP 3) used in Example 3 were mixed at a weight ratio of 60:40. Then, the mixture and propylene glycol monomethyl ether acetate (PGMEA) were mixed at a weight ratio of 16.91:83.09 to prepare 100 g of a resin composition.

[0123] Comparative Example 2

[0124] A resin composition was prepared by mixing the polymer manufactured in Synthesis Example 2 and propylene glycol monomethyl ether acetate (PGMEA) in a weight ratio of 13.76:86.24.

[0125]

[0126] [Experimental Example]

[0127] 1. Haze Measurement - Transparency Evaluation

[0128] The compositions manufactured in the above examples and comparative examples were evaluated for transparency by measuring the haze in a solution state. Specifically, the haze was measured at 23°C using a diffusion characteristic analysis system equipment (Nippon Denshoku, NDH-5000). If the haze value was "0", it was evaluated as having excellent transparency (◎). If there is haze, suspension and precipitation of the resin composition occur, and process stability deteriorates, so the haze value is required to be 0.

[0129] 2. Measurement of etch rate

[0130] We requested the Nano Comprehensive Technology Center (NNFC) to conduct CF4gas and O2N2gas etching evaluations, and measured the etching rate (E / R). The thickness was based on 4000Å, and the equipment used for the measurement was LAM's TCP-9400 DFM.

[0131] 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.

[0132] 3. Coating evaluation

[0133] Using 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, the coating performance was evaluated as excellent (◎).

[0134] The results according to the experimental examples 1 to 3 using the resin compositions manufactured in Examples 1 to 6 and Comparative Examples 1 to 2 are shown in Table 1 below.

[0135] [Table 1]

[0136]

[0137] As can be seen from Table 1 above, Examples 1 to 6 according to the present invention all exhibited excellent coatability and transparency, and it was confirmed that the etching resistance performance was also significantly improved compared to Comparative Examples 1 and 2.

[0138] Although the present invention has been described in more detail with reference to the embodiments of this specification, this specification is not necessarily limited to these embodiments, and various modifications may be implemented 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 to explain it, and the scope of the technical spirit of this specification is not limited by these embodiments. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. The scope of protection of this specification should be interpreted by the claims, and all technical ideas within a scope equivalent thereto should be interpreted as being included in the scope of rights of this specification.

Claims

1. Polymer for carbon hard mask; An insoluble zirconia compound having an average diameter of 1 nm to 50 nm; and containing an organic solvent; Highly transparent resin composition for hard mask.

2. In paragraph 1, A highly transparent resin composition for a hard mask, wherein the polymer for the carbon hard mask comprises a polymer represented by the following chemical formula 1 or chemical formula 2. [Chemical Formula 1] [Chemical formula 2] R1 in chemical formula 1 are the same or different from each other, and are each independently selected from hydrogen, a hydroxyl group, a C1-C10 alkyl group, a C6-C10 aryl group, a C3-C10 allyl group, and a halogen atom, R3 in chemical formula 2 are the same or different from each other, and each independently represents hydrogen, a hydroxyl group and -C p H 2p is selected from O, and p is an integer from 1 to 7, R2 of Chemical Formula 1 and / or Chemical Formula 2 are the same as or different from each other, and each independently represents one of the compound groups represented by the following Chemical Formulas (1-1) to (1-5), n and m are repeating units and are each independently an integer from 1 to 100. [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 1-4] [Chemical Formula 1-5] 3. In paragraph 2, In the above chemical formula 1, at least one of R2 comprises a compound group represented by the above chemical formula 1-5. Highly transparent resin composition for hard mask.

4. In paragraph 2, In the above chemical formula 2, at least one of R2 comprises a compound group represented by the above chemical formula 1-5. Highly transparent resin composition for hard mask.

5. In paragraph 1, A highly transparent resin composition for a hard mask, wherein the weight average molecular weight of the polymer for the carbon hard mask is 2,000 to 5,000.

6. In paragraph 1, The above insoluble zirconia compound is a highly transparent resin composition for a hard mask, wherein zirconia is surface-treated with a hydrophobic surface treatment agent.

7. In paragraph 6, A highly transparent resin composition for a hard mask, wherein the hydrophobic surface treatment agent is a silane coupling agent containing an alkoxy group.

8. In paragraph 7, A highly transparent, water-soluble composition for a hard mask, wherein the silane coupling agent is selected from alkyltrimethoxysilane and alkyltriethoxysilane represented by the following chemical formula 3. [Chemical Formula 3] Si(X)3(Y) In the above chemical formula 3, X is a methoxy group or an ethoxy group, and Y is a C1-C7 straight-chain alkyl group.

9. In paragraph 1, A high-transparency resin composition for a hard mask, comprising 0.1 to 40 wt% of the insoluble zirconia compound when the high-transparency resin composition for a hard mask is 100 wt%.

10. In paragraph 1, A highly transparent resin composition for a hard mask, wherein the organic solvent comprises at least one of tetrahydronaphthalene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, propylene glycol n-propyl ether, dimethyl formamide, gamma-butyrolactone, ethoxyethanol, methoxyethanol, methyl-3-methoxypropionate, and ethyl-3-ethoxypropionate.

11. A method for forming a semiconductor element pattern using a high-transparency resin composition for a hard mask according to any one of claims 1 to 10.

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