KR20210116085A - Resist underlayer composition, and method of forming patterns using the composition - Google Patents

Abstract

Provided are a composition for a resist underlayer film comprising a polymer including a structural unit represented by chemical formula 1, and a solvent, and a pattern forming method using the composition for a resist underlayer film. In the chemical formula 1, each substituent is as defined in the specification.

Description

Composition for resist underlayer and pattern formation method using same

The present disclosure relates to a composition for a resist underlayer and a pattern forming method using the same.

Recently, the semiconductor industry has developed from a pattern of several hundreds of nanometers to an ultra-fine technology having a pattern of several to tens of nanometers. An effective lithographic technique is essential to realize such ultra-fine technology.

The exposure process performed in the photoresist pattern formation step is one of the important factors for obtaining a high-resolution photoresist image.

As semiconductor patterns are gradually refined, the activation radiation used for photoresist exposure is also expanding to shorter wavelengths such as i-line (365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and EUV ( Extreme Ultraviolet), the need for a resist underlayer that can be applied to a patterning process to form an ultra-fine pattern in the 10 nm range using a light source is increasing.

In particular, the resist underlayer film needs to have a high etch selectivity with the photoresist, chemical resistance to the solvent used in the process after thermal curing during the process is required, and excellent adhesion to the resist film is required. However, many studies are being conducted to solve this problem.

A composition for a resist underlayer film exhibiting improved EUV absorption efficiency and/or improved film density is provided.

Another embodiment provides a pattern forming method using the composition for a resist underlayer.

According to one embodiment, there is provided a composition for a resist underlayer film comprising a polymer including a structural unit represented by the following Chemical Formula 1, and a solvent.

[Formula 1]

In Formula 1 or Formula 2,

A is a trivalent aromatic ring group or a trivalent heteroaromatic ring group,

R ₁ and R ₂ are each a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkenyl group, a substituted or unsubstituted C1 to C10 alkynyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group , substituted or unsubstituted C1 to C10 heteroalkenyl group, substituted or unsubstituted C1 to C10 heteroalkynyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C2 to C20 heterocycloalkyl group, substituted or An unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C1 to C20 heteroaryl group, or a functional group represented by the following formula K, wherein at least one of _{R 1} and R _{2 is a functional group represented by the following formula K,} * is the connection point,

[Formula K]

In the above formula (K),

L is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C1 to C10 heteroarylene group,

R _k is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, substituted Or an unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C1 to C20 heteroaryl group,

X is I, Br, Cl, or F, and * is a point connected to A in Formula 1 above.

According to another embodiment, forming an etch target film on a substrate, applying the composition for a resist underlayer film according to an embodiment on the etch target film to form a resist underlayer film, forming a photoresist pattern on the resist underlayer film and sequentially etching the resist underlayer layer and the etch target layer using the photoresist pattern using an etching mask.

The composition for a resist underlayer according to the exemplary embodiment may exhibit improved light absorption efficiency for EUV, thereby improving the sensitivity of the photoresist.

1 to 5 are cross-sectional views for explaining a pattern forming method using a composition for a resist underlayer according to an exemplary embodiment.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art to which the present invention pertains can easily implement them. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

In order to clearly express the various layers and regions in the drawings, the thicknesses are enlarged, and the same reference numerals are given to similar parts throughout the specification. When a part, such as a layer, film, region, plate, etc., is "on" another part, it includes not only the case where it is "directly on" another part, but also the case where there is another part in between. Conversely, when we say that a part is "just above" another part, we mean that there is no other part in the middle.

Unless otherwise defined herein, 'substituted' means that a hydrogen atom in the compound is a halogen group (-F, -Br, -Cl, or -I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid or its salt, phosphoric acid or its salt, vinyl group, C1-C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C6 to C30 allyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalkenyl group, C6 to C15 cycloalkynyl group, C3 to C30 heterocycloalkyl group, and combinations thereof.

In addition, unless otherwise defined herein, 'hetero' means containing 1 to 3 heteroatoms selected from N, O, S and P.

Unless otherwise specified herein, the weight average molecular weight is measured by dissolving a powder sample in tetrahydrofuran (THF) and then using Agilent Technologies' 1200 series Gel Permeation Chromatography (GPC) (column is Shodex). Company LF-804, standard sample is Shodex polystyrene).

Hereinafter, a composition for a resist underlayer film according to an embodiment will be described.

A composition for a resist underlayer according to an embodiment includes a polymer including a structural unit represented by the following Chemical Formula 1, and a solvent.

[Formula 1]

A is a trivalent aromatic ring group or a trivalent heteroaromatic ring group,

R ₁ and R ₂ are each a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkenyl group, a substituted or unsubstituted C1 to C10 alkynyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group , substituted or unsubstituted C1 to C10 heteroalkenyl group, substituted or unsubstituted C1 to C10 heteroalkynyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C2 to C20 heterocycloalkyl group, substituted or An unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C1 to C20 heteroaryl group, or a functional group represented by the following formula K, wherein at least one of _{R 1} and R _{2 is a functional group represented by the following formula K,} * is the connection point,

[Formula K]

In the above formula (K),

L is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C1 to C10 heteroarylene group,

R _k is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, substituted Or an unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C1 to C20 heteroaryl group,

X is I, Br, Cl, or F, and * is a point connected to A in Formula 1 above.

In one embodiment, R _k in Formula K may be hydrogen or another functional group substituted with a hydroxyl group. Specifically, R _k is hydrogen, a C1 to C10 alkyl group substituted with a hydroxyl group, a C1 to C10 heteroalkyl group substituted with a hydroxyl group, a C3 to C20 cycloalkyl group substituted with a hydroxyl group, a C2 to C20 heterocycloalkyl group substituted with a hydroxyl group, a hydroxyl group It may be a substituted C6 to C20 aryl group, or a C1 to C20 heteroaryl group substituted with a hydroxyl group. More specifically, R _k may be hydrogen, a C1 to C10 alkyl group substituted with a hydroxyl group, or a C1 to C10 heteroalkyl group substituted with a hydroxyl group.

In one embodiment, A may be a trivalent heteroaromatic ring group, and the trivalent heteroaromatic ring group may be a trivalent nitrogen-containing heteroaromatic ring group.

Specifically, A may be represented by at least one of the following Chemical Formula A-1 or Chemical Formula A-2.

[Formula A-1]

[Formula A-2]

In Formulas A-1 and A-2, * is a connection point.

In one embodiment, the polymer may be represented by the following Chemical Formula 1-1 or the following Chemical Formula 1-2.

[Formula 1-1]

[Formula 1-2]

In Formula 1-1 and Formula 1-2,

R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , and R ₂₅ are each independently, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkenyl group, a substituted or unsubstituted C1 to C10 alkynyl group, a substituted or unsubstituted A substituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C1 to C10 heteroalkenyl group, a substituted or unsubstituted C1 to C10 heteroalkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to A C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C1 to C20 heteroaryl group, or a functional group represented by Formula K, R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ At least one of, R ₂₁ , R ₂₂ , At least one of R ₂₃ , and R ₂₄ is each a functional group represented by Formula K,

R ₁₆ and R ₂₆ are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkenyl group, a substituted or unsubstituted C1 to C10 alkynyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, substituted or unsubstituted C1 to C10 heteroalkenyl group, substituted or unsubstituted C1 to C10 heteroalkynyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C2 to C20 hetero a cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C1 to C20 heteroaryl group, or a functional group represented by the above formula (K);

m1, n1, m2, and n2 are each an integer from 0 to 100, wherein m1 + n1 > 0 and m2 + n2 > 0.

In one embodiment, at least one of _{R 11} , R ₁₂ , R ₁₃ , and R _{14 and R 21} , R ₂₂ , At least one of R ₂₃ and R ₂₄ may be a substituted or unsubstituted C1 to C10 alkenyl group, or a substituted or unsubstituted C1 to C10 heteroalkenyl group. For example, at least one of _{R 11} , R ₁₂ , R ₁₃ , and R _{14 and R 21} , R ₂₂ , At least one of R ₂₃ and R ₂₄ may be a substituted or unsubstituted C1 to C10 alkenyl group.

Specifically, in Formula 1-1 and Formula 1-2, R ₁₁ , R ₁₂ , R ₁₃ , and at least one of the functional groups that come to _{R 14 and R 21} , R ₂₂ , At least one of the functional groups coming to R ₂₃ , and R ₂₄ is a functional group represented by the aforementioned formula K, respectively, and at least one of the other functional groups is the aforementioned substituted or unsubstituted C1 to C10 alkenyl group, or a substituted or It may be a functional group including a double bond, such as an unsubstituted C1 to C10 heteroalkenyl group.

In this case, R _11, R _12, R _13, and, based on the total mole number of R _14, R _11, R _12, R _13, and R ₁₄ from a substituted or unsubstituted C1 to C10 alkenyl group, or a substituted or unsubstituted The ratio of the number of moles of the functional group substituted with the cyclic C1 to C10 heteroalkenyl group may be 1% to 50%, for example, 5% to 30%.

In one embodiment, R _21, R _22, R _23, and with respect to the number chongmol of R _24, R _21, R _22, R _23, and R ₂₄ from a substituted or unsubstituted C1 to C10 alkenyl group, or a substituted or The ratio of the number of moles of the functional group substituted with the unsubstituted C1 to C10 heteroalkenyl group may be 1% to 50%, for example, 5% to 30%.

On the other _{hand, R 11, R 12, R} 13, and, based on the total mole number of R _{14, R 11, R 12, R} 13, and R ₁₄ molar ratio of the number of the functional group represented by the general formula K is 3% to 90%, such may be in the example 5% to _{50%, R 21, R 22} , R 23, and with respect to R ₂₄ total mole number of, R _21, R _22, R _23, and R ₂₄ in the formula, K The ratio of the number of moles of the functional group represented by may be 3% to 90%, for example, 5% to 50%.

Meanwhile, the polymer including the structural unit may be represented by any one of Chemical Formulas 2 to 6 below.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In Formula 2 to Formula 6,

m, and n are each independently an integer from 0 to 100, wherein m + n > 0.

For example, an aromatic or heteroaromatic compound in which the polymer constituting the resist underlayer composition is connected to a functional group represented by the above formula K, for example, a heteroalkylene group (including -O-) containing a halogen group ( For example, when an isocyanurate-based compound or a triazine-based compound) is included, the aromatic or heteroaromatic compound may improve light absorption efficiency of an exposure light source during exposure of the resist underlayer composition.

On the other hand, a polymer including an aromatic or heteroaromatic compound having a hydroxyl group (-OH) introduced therein has an effect of increasing the film density of the resist underlayer film composition by increasing the crosslinking density. The resist underlayer film composition according to an embodiment exhibits improved adhesion with the upper photoresist due to the increased film density as described above, and may exhibit improved chemical resistance against cold to a solvent used during the coating process of the upper photoresist. . Therefore, by using the high-density resist underlayer composition according to the embodiment, it is possible to form a resist underlayer film having improved adhesion and chemical resistance and a reduced thickness, and through this, a faster etching effect can be expected compared to the upper photoresist.

In one embodiment, when the resist underlayer film is formed using the resist underlayer film composition, secondary electrons may be additionally generated during the photo process. The additionally generated secondary electrons may affect the photoresist during the photo process to maximize the acid generation efficiency. Accordingly, the photoresist sensitivity may be improved by improving the photo process speed of the photoresist.

In addition, even if the polymer including the aromatic or heteroaromatic compound (eg, isocyanurate compound or triazine compound) is polymerized in a state with a relatively high molecular weight, solubility in organic solvents such as propylene glycol methyl ether (PGME) is excellent Accordingly, the resist underlayer film composition may exhibit excellent coatability due to excellent solubility with the organic solvent.

In addition, since the polymer is stable with respect to organic solvents and heat, when the resist underlayer film is formed using the composition for a resist underlayer film containing the polymer, during the process for forming the photoresist pattern, it is peeled off by solvent or heat or It is possible to minimize the generation of by-products due to the generation of chemical substances, etc., and also minimize the thickness loss due to the photoresist solvent on the upper part.

On the other hand, the polymer may include sulfur (S) in the main chain. In this case, a relatively high refractive index may be realized, and a faster etching rate may be exhibited together.

In addition, the polymer has excellent solubility and can form a resist underlayer film having excellent coating uniformity. It is possible to form a uniform thin film without deterioration of the substrate and provide excellent gap-fill and planarization characteristics when a step exists in the lower substrate (or film) or when a pattern is formed.

The composition for a resist underlayer according to the exemplary embodiment has excellent coating uniformity, excellent stability, high refractive index, and fast etching rate, so it can be applied to EUV (Extreme Ultraviolet) lithography process. The EUV lithography process is a lithography technique using light of a very short wavelength such as 10 nm to 20 nm, for example 13.5 nm, and is a process capable of forming an ultra-fine pattern having a width of 20 nm or less.

Meanwhile, the polymer may have a weight average molecular weight (Mw) of 1,000 g/mol to 100,000 g/mol. More specifically, the polymer may have a weight average molecular weight of 1,000 g/mol to 50,000 g/mol, or 1,000 g/mol to 30,000 g/mol. By having a weight average molecular weight in the above range, it can be optimized by controlling the carbon content and solubility in a solvent of the composition for a resist underlayer including the polymer.

The solvent is not particularly limited as long as it has sufficient solubility or dispersibility for the polymer, but for example, propylene glycol, propylene glycol diacetate, methoxy propanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) mono Methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, methylpyrrolidone , methylpyrrolidinone, acetylacetone, and ethyl 3-ethoxypropionate may include at least one selected from the group consisting of propionate.

The polymer may be included in an amount of 0.1 to 50% by weight, 0.1 to 30% by weight, or 0.1 to 15% by weight based on the total content of the composition for the resist underlayer. By being included in the above range, the thickness, surface roughness, and planarization degree of the resist underlayer can be adjusted.

In addition, the composition for the resist underlayer may further include at least one other polymer selected from among an acrylic resin, an epoxy resin, a novolak resin, a glucoluryl resin, and a melamine resin, in addition to the above-described polymer, but is not limited thereto. .

The composition for the resist underlayer may further include an additive of a surfactant, a thermal acid generator, a plasticizer, or a combination thereof.

The surfactant may be, for example, an alkylbenzenesulfonic acid salt, an alkylpyridinium salt, polyethylene glycol, a quaternary ammonium salt, and the like, but is not limited thereto.

The thermal acid generator is, for example, an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid, and/or benzointosyl Late, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters may be used, but the present invention is not limited thereto.

The additive may be included in an amount of 0.001 to 40 parts by weight based on 100 parts by weight of the composition for resist underlayer. By including it in the said range, solubility can be improved without changing the optical characteristic of the composition for resist underlayer films.

According to another embodiment, a resist underlayer film prepared by using the above-described composition for a resist underlayer film is provided. The resist underlayer film may be in a form that is cured through a heat treatment process after coating the above-described composition for a resist underlayer film on, for example, a substrate.

Hereinafter, a method of forming a pattern using the above-described composition for a resist underlayer film will be described with reference to FIGS. 1 to 5 .

1 to 5 are cross-sectional views for explaining a pattern forming method using the composition for a resist underlayer according to the present invention.

Referring to FIG. 1 , first, an object to be etched is prepared. An example of the object to be etched may be the thin film 102 formed on the semiconductor substrate 100 . Hereinafter, only the case where the object to be etched is the thin film 102 will be described. In order to remove contaminants and the like remaining on the thin film 102, the thin film surface is pre-cleaned. The thin film 102 may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.

Then, a composition for a resist underlayer film comprising a solvent and a polymer having moieties represented by Chemical Formulas 1 and 2 is coated on the surface of the cleaned thin film 102 by applying a spin coating method.

Thereafter, a drying and baking process is performed to form the resist underlayer 104 on the thin film. The baking treatment may be performed at 100° C. to 500° C., for example, at 100° C. to 300° C. A more specific description of the composition for a resist underlayer film is omitted in order to avoid duplication because it has been described in detail above.

Referring to FIG. 2 , a photoresist layer 106 is formed by coating a photoresist on the resist underlayer layer 104 .

Examples of the photoresist include a positive photoresist containing a naphthoquinonediazide compound and a novolak resin, an acid generator capable of dissociating an acid upon exposure, and decomposition in the presence of an acid to increase solubility in an alkaline aqueous solution and thus to a compound and A chemically amplified positive photoresist containing an alkali-soluble resin, a chemically amplified positive photoresist containing an alkali-soluble resin having a group capable of imparting a resin that increases solubility in aqueous alkali solution by decomposition in the presence of an acid generator and acid type photoresist and the like.

Next, a first baking process of heating the substrate 100 on which the photoresist film 106 is formed is performed. The first baking process may be performed at a temperature of 90 °C to 120 °C.

Referring to FIG. 3 , the photoresist layer 106 is selectively exposed.

An exposure process for exposing the photoresist film 106 is described as an example, an exposure mask having a predetermined pattern formed thereon is placed on a mask stage of an exposure apparatus, and the exposure mask ( 110) are sorted. Then, by irradiating light to the mask 110 , a predetermined portion of the photoresist film 106 formed on the substrate 100 selectively reacts with the light passing through the exposure mask.

For example, examples of the light that can be used in the exposure process include an i-line activating radiation having a wavelength of 365 nm, a KrF excimer laser having a wavelength of 248 nm, and short-wavelength light such as an ArF excimer laser having a wavelength of 193 nm. In addition, extreme ultraviolet (EUV) light having a wavelength of 13.5 nm corresponding to extreme ultraviolet light may be used.

The photoresist film 106a of the exposed portion has a relatively hydrophilicity compared to the photoresist film 106b of the unexposed portion. Accordingly, the photoresist film of the exposed portion 106a and the non-exposed portion 106b has different solubility.

Next, a second baking process is performed on the substrate 100 . The second baking process may be performed at a temperature of 90 °C to 150 °C. By performing the second baking process, the photoresist film corresponding to the exposed region is easily dissolved in a specific solvent.

Referring to FIG. 4 , a photoresist pattern 108 is formed by dissolving and then removing the photoresist layer 106a corresponding to the exposed area using a developer. Specifically, the photoresist pattern 108 is completed by dissolving and removing the photoresist layer corresponding to the exposed area using a developer such as tetra-methyl ammonium hydroxide (TMAH).

Next, the resist underlayer layer is etched using the photoresist pattern 108 as an etching mask. The organic layer pattern 112 is formed through the etching process as described above. The etching may be performed, for example, by dry etching using an etching gas, and the etching gas may be, for example, CHF ₃ , CF ₄ , Cl ₂ , O _{2 ,} or a mixture thereof. As described above, since the resist underlayer film formed by the resist underlayer film composition according to the exemplary embodiment has a fast etching rate, a smooth etching process can be performed within a short time.

Referring to FIG. 5 , the exposed thin film 102 is etched by applying the photoresist pattern 108 as an etching mask. As a result, the thin film is formed as a thin film pattern 114 . In the exposure process performed above, the thin film pattern 114 formed by the exposure process performed using a short-wavelength light source such as an activating radiation i-line (365 nm), a KrF excimer laser (wavelength 248 nm), and an ArF excimer laser (wavelength 193 nm). ) may have a width of several tens of nm to several hundred nm, and the thin film pattern 114 formed by an exposure process performed using an EUV light source may have a width of 20 nm or less.

Hereinafter, the present invention will be described in more detail through examples relating to the synthesis of the above-described polymer and the preparation of a composition for a resist underlayer film comprising the same. However, the present invention is not technically limited by the following examples.

Synthesis example

Synthesis Example 1

171 g (m = 80, n = 20) of the resin represented by the following Chemical Formula A, 169 g of iodosuccinimide, 369 g of acetonitrile, and 396 g of distilled water were put into a reactor and dissolved.

[Formula A]

Thereafter, the reaction solution was heated to 80° C. and stirred for 24 hours. Then, after the reaction solution was lowered to room temperature, _{500 mL of a 10% Na 2} S ₂ O ₅ aqueous solution was added and stirred for 3 hours. After that, 1 L of distilled water is further added to the stirred mixture, filtered, and the precipitate is collected and the remaining solution is discarded.

The obtained precipitate was added to 1 L of distilled water and then again stirred and filtered to take the precipitate and discard the residual solution, thereby obtaining a polymer represented by the following Chemical Formula 2 (m = 80, n = 20 , Mw = 5,800 g/mol) .

[Formula 2]

Synthesis Example 2

Preparation of a reaction solution by dissolving 102 g of the resin represented by Formula A of Synthesis Example 1 (m = 80, n = 20), 101 g of N-bromosuccinimide, 355 g of hexanediol, and 1303 g of acetonitrile in a reactor Except for that, a polymer (m=80, n=20, Mw=6,100 g/mol) represented by the following Chemical Formula 3 was obtained through the same process as in Synthesis Example 1.

[Formula 3]

Synthesis Example 3

103 g of a resin represented by the following Chemical Formula B (m = 90, n = 10) and N-bromosuccinimide A polymer represented by the following Chemical Formula 4 (m = 90, n = 10 through the same process as in Synthesis Example 1 except for preparing a reaction solution by dissolving 121 g, 370 g of distilled water, and 428 g of acetonitrile in a reactor. , Mw= 12,100 g/mol) was obtained.

[Formula B]

[Formula 4]

Synthesis Example 4

101 g (m = 90, n = 10) of the resin represented by Formula A of Synthesis Example 1, 97 g of N-chlorosuccinimide, 247 g of butanediol, and acetonitrile A polymer represented by the following Chemical Formula 5 (m = 90, n = 10 , Mw = 8,500 g/mol) was obtained.

[Formula 5]

Synthesis Example 5

112 g of the resin represented by Formula A of Synthesis Example 1 (m = 90, n = 10) and N-fluorobenzenesulfonimide 283 g, distilled water 640 g, and acetonitrile A polymer represented by the following Chemical Formula 6 (m = 90, n = 10, Mw = 8,900 g/mol) was obtained through the same process as in Synthesis Example 1 except for preparing a reaction solution by dissolving 1,050 g in a reactor. .

[Formula 6]

Comparative Synthesis Example

A polymer including a structural unit represented by the following Chemical Formula 7 was synthesized by the method disclosed in Scheme 1 below.

[Scheme 1]

Specifically, 25.5 g of monomethyldiglycidylisocyanuric acid, 16.6 g of terephthalic acid, and _{0.54 g of benzyltriethylammonium chloride (BnEt 3} NCl) were dissolved in 100 g of propylene glycol monomethyl ether (PGMEA), and then 130 ° C. A polymer (Mw = 7,600 g/mol) including a structural unit represented by the following Chemical Formula 7 was obtained by reacting for 24 hours.

[Formula 7]

Preparation of a composition for a resist underlayer film

Examples 1 to 5 and Comparative Examples

For each of the polymers prepared in Synthesis Examples 1 to 5 and Comparative Synthesis Examples, 0.5 g of the polymer, 0.125 g of PD1174 (TCI Corporation; curing agent), and 0.125 g of pyridinium para-toluenesulfonate (PPTS) together with propylene Compositions for resist underlayers according to Examples 1 to 5 and Comparative Examples were prepared by completely dissolving in 100 g of a mixed solvent of glycol monomethyl ether and ethyl lactate (mixing volume ratio = 7:3), respectively.

Membrane density evaluation

The compositions for resist underlayer films according to Examples 1 to 5 and Comparative Examples were respectively coated on a silicon substrate by a spin-on coating method, and then heat-treated on a hot plate at 205° C. for 1 minute to form a resist underlayer film with a thickness of about 100 nm. .

Next, the density of the resist underlayer was measured, and the results are shown in Table 1. The density of the resist underlayer film was measured using an X-Ray Diffractometer (Model: X'Pert PRO MPD, Panalytical Co.).

Membrane density (g/cm ³ ) Example 1 1.52 Example 2 1.35 Example 3 1.44 Example 4 1.38 Example 5 1.45 comparative example 1.21

Referring to Table 1, it can be seen that the film formed using the composition for the resist underlayer film according to Examples 1 to 5 has a higher density than the film formed using the composition for the resist underlayer film according to Comparative Example. Therefore, from the results of Table 1, it can be seen that when the compositions for resist underlayer films according to Examples 1 to 5 are used, a film having a more dense structure can be formed compared to the comparative example.

Exposure characteristics evaluation

After each of the compositions prepared in Examples 1 to 5 and Comparative Examples were coated by a spin-on coating method, heat treatment was performed at 205° C. for 50 seconds on a hot plate to form a resist underlayer film having a thickness of about 10 nm.

Thereafter, a photoresist solution was applied on the photoresist underlayer by a spin-on coating method, and then a photoresist layer was formed by heat treatment at 110° C. for 1 minute on a hot plate. The photoresist layer was exposed to an acceleration voltage of 100 keV using an e-beam exposure machine (Elionix), and then heat-treated at 110° C. for 60 seconds. Subsequently, the photoresist layer was developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23° C. and then rinsed in pure water for 15 seconds to form a line and space (L/S) photoresist pattern. was formed.

Next, the optimal exposure dose, resolution, and development residue of the photoresist pattern were evaluated, and the results are shown in Table 2.

Here, the exposure dose for resolving the 100 nm line and space 1:1 is called the optimal exposure dose (Eop, μC/cm 2 ), and the minimum line width of the line and space at the optimum exposure dose is called the resolution. The resolution was measured using a scanning electron microscope (SEM) S-9260 (Hitachi Corporation) for limit resolution (nm).

The developing residue is based on a dissolution rate (DR) of a 2.38 mass% aqueous solution of tetramethyl ammonium hydroxide (TMAH), and the faster the rate, the more the developing residue after pattern formation (eg, line width roughness, line width roughness). ) decreased and the degree of the decrease was observed with a scanning electron microscope (SEM) and expressed as ○ for good, △ for poor, and X for poor (bridge formation).

Eop (compared to Example 1) Resolution (nm) development residue state Example 1 1.00 36 ○ Example 2 1.16 39 ○ Example 3 0.96 35 ○ Example 4 1.12 36 ○ Example 5 1.03 32 ○ comparative example 1.34 46 △

Referring to Table 2, when the resist underlayer film was formed using the composition for the photoresist underlayer film according to Examples 1 to 5, the optimal exposure amount, resolution, and development residue state of the photoresist pattern were all excellent compared to Comparative Examples. Therefore, from the results of Table 2, it can be seen that, when the compositions for resist underlayer films according to Examples 1 to 5 are used, a photoresist pattern having better sensitivity than that of Comparative Example can be formed.

In the foregoing, specific embodiments of the present invention have been described and shown, but it is common knowledge in the art that the present invention is not limited to the described embodiments, and that various modifications and variations can be made without departing from the spirit and scope of the present invention. It is self-evident to those who have Accordingly, such modifications or variations should not be individually understood from the technical spirit or point of view of the present invention, and modified embodiments should be said to belong to the claims of the present invention.

100: substrate 102: thin film
104: resist underlayer film 106: photoresist film
108: photoresist pattern 110: mask
112: organic film pattern 114: thin film pattern

Claims (17)

A polymer comprising a structural unit represented by the following formula (1); and
menstruum
A composition for a resist underlayer comprising:
[Formula 1]

In Formula 1 or Formula 2,
A is a trivalent aromatic ring group or a trivalent heteroaromatic ring group,
R ₁ and R ₂ are each a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkenyl group, a substituted or unsubstituted C1 to C10 alkynyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group , substituted or unsubstituted C1 to C10 heteroalkenyl group, substituted or unsubstituted C1 to C10 heteroalkynyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C2 to C20 heterocycloalkyl group, substituted or An unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C1 to C20 heteroaryl group, or a functional group represented by the following formula K, wherein at least one of _{R 1} and R _{2 is a functional group represented by the following formula K,} * is the connection point,
[Formula K]

In the above formula (K),
L is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C1 to C10 heteroalkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C2 to C20 heterocycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C1 to C10 heteroarylene group,
R _k is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, substituted Or an unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C1 to C20 heteroaryl group,
X is I, Br, Cl, or F, and * is a point connected to A in Formula 1 above. In claim 1,
Wherein A is a composition for a resist underlayer film represented by at least one of the following Chemical Formula A-1 or Chemical Formula A-2:
[Formula A-1]

[Formula A-2]

In Formulas A-1 and A-2, * is a connection point. In claim 1,
The polymer is a composition for a resist underlayer film represented by the following Chemical Formula 1-1 or the following Chemical Formula 1-2:
[Formula 1-1]

[Formula 1-2]

In Formula 1-1 and Formula 1-2,
R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , and R ₂₅ are each independently, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkenyl group, a substituted or unsubstituted C1 to C10 alkynyl group, a substituted or unsubstituted A substituted C1 to C10 heteroalkyl group, a substituted or unsubstituted C1 to C10 heteroalkenyl group, a substituted or unsubstituted C1 to C10 heteroalkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to A C20 heterocycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C1 to C20 heteroaryl group, or a functional group represented by Formula K, R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ At least one of, R ₂₁ , R ₂₂ , At least one of R ₂₃ , and R ₂₄ is each a functional group represented by Formula K,
R ₁₆ and R ₂₆ are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkenyl group, a substituted or unsubstituted C1 to C10 alkynyl group, a substituted or unsubstituted C1 to C10 heteroalkyl group, substituted or unsubstituted C1 to C10 heteroalkenyl group, substituted or unsubstituted C1 to C10 heteroalkynyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C2 to C20 hetero a cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C1 to C20 heteroaryl group, or a functional group represented by the above formula (K);
m1, n1, m2, and n2 are each an integer from 0 to 100, wherein m1 + n1 > 0 and m2 + n2 > 0. In claim 3,
at least one of R ₁₁ , R ₁₂ , R ₁₃ , and R _{14 and R 21} , R ₂₂ , At least one of R ₂₃ and R ₂₄ is a substituted or unsubstituted C1 to C10 alkenyl group, or a substituted or unsubstituted C1 to C10 heteroalkenyl group. In claim 4,
R _11, R _12, R _13, and R ₁₄ with respect to the total mole number of R _11, R _12, R _13, and R ₁₄ from a substituted or unsubstituted C1 to C10 alkenyl group, or a substituted or unsubstituted C1 The ratio of the number of moles of the functional groups substituted with to C10 heteroalkenyl groups is 1% to 50% of the composition for a resist underlayer film. In claim 4,
R _21, R _22, R _23, and R ₂₄ with respect to the total mole number of R _21, R _22, R _23, and R ₂₄ from a substituted or unsubstituted C1 to C10 alkenyl group, or a substituted or unsubstituted C1 The ratio of the number of moles of the functional groups substituted with to C10 heteroalkenyl groups is 1% to 50% of the composition for a resist underlayer film. In claim 3,
The ratio of the number of moles of the functional group represented by Formula K among R ₁₁ , R ₁₂ , R ₁₃ , and R _{14 to} the total number of moles of R ₁₁ , R ₁₂ , R ₁₃ , and R _{14 is 3% to 90%} A composition for a phosphor underlayer film. In claim 3,
The ratio of the number of moles of the functional group represented by Formula K among R ₂₁ , R ₂₂ , R ₂₃ , and R _{24 to} the total number of moles of R ₂₁ , R ₂₂ , R ₂₃ , and R _{24 is 3% to 90%} A composition for a phosphor underlayer film. In claim 1,
R _k is hydrogen, a C1 to C10 alkyl group substituted with a hydroxyl group, a C1 to C10 heteroalkyl group substituted with a hydroxyl group, a C3 to C20 cycloalkyl group substituted with a hydroxyl group, a C2 to C20 heterocycloalkyl group substituted with a hydroxyl group, a hydroxyl group A composition for a resist underlayer comprising a C6 to C20 aryl group or a C1 to C20 heteroaryl group substituted with a hydroxyl group. In claim 1,
The polymer is a composition for a resist underlayer film represented by any one of the following Chemical Formulas 2 to 6:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In Formula 2 to Formula 6,
m, and n are each independently an integer from 0 to 100, wherein m + n > 0. In claim 1,
The weight average molecular weight of the polymer is 1,000 g / mol to 100,000 g / mol of the resist underlayer composition. In claim 1,
The polymer is included in an amount of 0.1 wt% to 50 wt% based on 100 wt% of the composition for the resist underlayer film. In claim 1,
A resist underlayer composition further comprising at least one polymer selected from an acrylic resin, an epoxy resin, a novolak resin, a glycoluril resin, and a melamine resin. In claim 1,
A composition for a resist underlayer further comprising an additive including a surfactant, a thermal acid generator, a plasticizer, or a combination thereof. forming a film to be etched on the substrate;
Forming a resist underlayer film by applying the composition for a resist underlayer film according to any one of claims 1 to 14 on the etch target film;
forming a photoresist pattern on the resist underlayer; and
sequentially etching the resist underlayer layer and the etch target layer using the photoresist pattern as an etching mask
A pattern forming method comprising a. In claim 15,
Forming the photoresist pattern is
forming a photoresist film on the resist underlayer film;
exposing the photoresist film; and
and developing the photoresist film. In claim 15,
The step of forming the resist underlayer film further comprises the step of heat-treating at a temperature of 100 °C to 500 °C after coating the composition for the resist underlayer film.

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