TW201903031A - Composition for producing organic anti-reflective film having high etch rate being useful in simplification of processes and excellent in a pattern profile - Google Patents

Abstract

Disclosed is a composition for producing an organic anti-reflective film which has an anti-reflective function, is useful in simplification of processes, is excellent in a pattern profile, and has a high etch rate, and a production method therefor. The disclosed composition for producing an organic anti-reflective film comprises: an anti-reflective polymer comprising repeating units represented by the following chemical formulae 1-1, 1-2 and 1-3; an isocyanurate compound comprising at least one portion represented by the following chemical formula 2; and an organic solvent for dissolving the aforementioned ingredients, chemical formulae 1-1, 1-2, 1-3, and 2. In chemical formulae 1-1 to 1-3, R1 is each independently a hydrogen or methyl, R2 is hydrogen, methyl or a C1 to C5 hydrocarbon group having 0 to 2 heteroatoms, R3 is a C1 to C12 hydrocarbon group having 0 to 2 heteroatoms without any chromophore, R4 is a chromophore-containing hydrocarbon group as a C6 to C20, chain or cyclic and saturated or unsaturated hydrocarbon group having 0 to 2 heteroatoms. In chemical formula 2, R is hydrogen or methyl, R' is each independently a C1 to C15 chain or C3 to C15 cyclic, and saturated or unsaturated hydrocarbon group having 0 to 6 heteroatoms, R'' is a C1 to C15 chain or C3 to C15 cyclic, and saturated or unsaturated hydrocarbon group having 0 to 8 heteroatoms, R''' is each independently NH or O. R* is each independently S or O, and adjacent functional groups have the same element. Two or more portions represented by chemical formula 2 may be connected by R'. X, y and z are the molar percent of the repeating units constituting the polymer, in which x is from 30 to 50 mol%, y is 10 to 50 mol%, and z is 10 to 50 mol%.

Description

Composition for forming an organic anti-reflection film having a high etching rate

The present invention relates to an organic anti-reflection film, and more particularly to a composition for forming an organic anti-reflection film which not only has a high etching rate but also simplifies the steps and reduces photoresist damage after etching.

In the photolithography step, in order to increase the limit resolution of the photoresist (PR) 10 pattern, an ArF (193 nm) excimer laser having a short wavelength is used as an exposure source. However, when the wavelength of the exposure source is shortened, an optical interference effect based on the reflected light reflected from the etched layer 30 of the semiconductor substrate increases, and the pattern profile is poor by undercutting, notching, or the like. Or the size uniformity is reduced. In order to prevent the above problem, an anti-reflective coating (bottom anti-reflective coatings (BARCs)) for absorbing exposure light (reflected light) is usually formed between the layer to be etched and the photoresist film. Such an antireflection film is classified into an inorganic antireflection film of titanium, titanium oxide, titanium nitride, chromium oxide, carbon, amorphous germanium or the like according to the kind of the substance to be used, and an organic antireflection formed of a polymer material. membrane. In general, an organic anti-reflection film has an advantage in that a vacuum evaporation device, a chemical vapor deposition (CVD) device, a sputtering device, and the like for forming a film are not required, compared to an inorganic anti-reflection film, and Excellent absorption of radiation, low molecular weight substances do not diffuse from the organic anti-reflection film to the photoresist film during heating, coating and drying, and in the dry etching step associated with the photoresist, the etching rate (etch Rate) Relatively excellent.

The conventional organic anti-reflection film has a problem of residual scum after the exposure step in the substrate having the height difference. In order to improve the problem, as shown in FIG. 1, a metal layer including a spin-on carbon (SOC) or an amorphous carbon layer (ACL) 22, an oxide (Oxide), or the like is introduced. (Metal Layer) 21 complex steps. This step (scheme) takes a long time to prepare a pattern due to the complicated number of steps, and is damaged by the photoresist when the etching step is performed, thereby having limitations in the steps. Thus, there is a need to develop a composition effective for forming an organic anti-reflection film in terms of step simplification.

Accordingly, it is an object of the present invention to provide a composition for forming an organic anti-reflection film which has a high etching rate in an etching step and has a high anti-reflection function.

Another object of the present invention is to provide a composition for forming an organic anti-reflection film which has a high etching rate to achieve simplification of the steps, and the photoresist has less damage after etching.

In order to achieve the object, the present invention provides a composition for forming an organic anti-reflection film, comprising: an antireflection polymer comprising a repeating unit represented by the following Chemical Formula 1-1, Chemical Formula 1-2, and Chemical Formula 1-3; The isocyanurate compound contains one or more moieties represented by the following Chemical Formula 2; and an organic solvent for dissolving the components.

Chemical formula 1-1:

Chemical formula 1-2:

Chemical formula 1-3:

Chemical formula 2:

In Chemical Formula 1-1 to Chemical Formula 1-3, R ₁ is hydrogen or methyl, R ₂ is hydrogen or a hydrocarbon group having 1 to 5 carbon atoms containing 0 to 2 hetero atoms, and R ₃ is a chromophore-free group. a hydrocarbon group having a carbon number of 1 to 12, and R ₄ is a chain or ring-shaped saturated or unsaturated hydrocarbon group having 6 to 20 carbon atoms containing 0 to 2 hetero atoms, and x, y, and z are used as constituent polymer repeating units. Moh ratio, independently, x is from 30 mole percent to 60 mole percent, y is from 0 mole percent to 50 mole percent, and z is from 10 mole percent to 50 mole percent.

In Chemical Formula 2, R is hydrogen or a methyl group, and R' is independently a chain having a carbon number of 1 to 15 containing 0 to 6 hetero atoms or a ring having a carbon number of 3 to 15 saturated or unsaturated. a hydrocarbon group, R'' is a chain of 1 to 15 or a ring-shaped saturated or unsaturated hydrocarbon group having 3 to 15 carbon atoms, and R''' is independently NH or O. R* is independently S or O, and adjacent functional groups have the same elements.

As the composition for forming an organic anti-reflection film based on the present invention, an organic anti-reflection film having an anti-reflection function and a high etching rate can be provided. Moreover, the simplification of the steps can be achieved by the organic anti-reflection film having a high etching rate, and the composition can be used to reduce the damage of the photoresist after etching.

Hereinafter, the present invention will be described in detail.

The composition for forming an organic anti-reflection film of the present invention has an anti-reflection film function and has a high etching rate, thereby serving as a composition for forming an organic anti-reflection film, which comprises an anti-reflection polymer, which can simplify the steps. , isocyanurate compounds and organic solvents.

The present invention has an anti-reflection film function at 193 nm and 248 nm wavelengths by including a gap-fill (void-free) property for a step having a height difference and a chromophore of a benzene ring or a fluorene structure. Thus, by effectively suppressing undercutting, notching, and footing based on reflected light, antireflection represented by the following Chemical Formula 1 is included as a profile for improving the pattern A polymer and a carbon-heteroatome bond, in particular, a carbon-oxygen bond, thereby using an isocyanurate represented by the following chemical formula 2 having a high etch rate (isocyanurate) A polymer of the type (Publication No. 10-2011-0028763), in the case where only an antireflection polymer is used, the etching rate is slow, so that when the etching step is performed, photoresist (PR) damage is generated. (damage) and leave scum in the topology section. Further, when only an isocyanurate polymer is used, there is a problem that a photoresist performance problem (PR performance issue) may occur due to insufficient antireflection function. By using such two kinds of polymers in combination, it has an anti-reflection function and forms an effective composition in terms of step simplification by a fast etching rate.

The antireflection polymer of the present invention includes a repeating unit represented by the following Chemical Formula 1-1 to Chemical Formula 1-3.

Chemical formula 1-1:

Chemical formula 1-2:

Chemical formula 1-3:

In Chemical Formula 1-1 to Chemical Formula 1-3, R _{1 is} each independently hydrogen or a methyl group, and R ₂ serves as a crosslinking agent, and is hydrogen or a hydrocarbon group having 1 to 5 carbon atoms containing 0 to 2 hetero atoms. Specifically, it is hydrogen or a hydrocarbon group having 1 to 3 carbon atoms containing 0 to 2 hetero atoms, for example, a hydrocarbon group having 1 to 3 carbon atoms containing hydrogen or a hydroxyl group (-OH) and/or an epoxy group And R ₃ functions as a spacer, and is a hydrocarbon group having 1 to 12 carbon atoms which does not contain a chromophore and contains 0 to 2 hetero atoms, specifically, a carbon number of 1 to 2 containing 0 to 2 hetero atoms. The hydrocarbon group of 10, more specifically, a hydrocarbon group having 1 to 8 carbon atoms containing 0 to 2 hetero atoms, particularly specifically a hydrocarbon group having 4 to 8 carbon atoms containing 0 to 2 hetero atoms.

Further, R _{4 is} a hydrocarbon group of a chromophore which functions to absorb the exposed light, and is a chain or ring-shaped saturated or unsaturated hydrocarbon group having 6 to 20 carbon atoms and containing 0 to 2 hetero atoms. Specifically, it is a chain or ring-shaped saturated or unsaturated hydrocarbon group having 6 to 16 carbon atoms containing 0 to 2 hetero atoms, more specifically, a carbon number of 6 to 16 containing 0 to 2 hetero atoms. The aryl group, most specifically, is an aryl group having 6 to 16 carbon atoms and containing 1 to 2 hetero atoms.

Specific examples of R ₂ include -H and -CH ₃ . , Etc., as a specific example of R ₃ , a exemplification , , v Specific examples of R 4 containing a chromophore include a functional group containing benzene or hydrazine, and specifically, a exemplified , , , , , Etc., by including a benzene ring or a ruthenium structure, absorb light under exposure conditions of 193 nm and 248 nm, and have an anti-reflection function.

In Chemical Formula 1-1 to Chemical Formula 1-3, x is 0% by mole to 70% by mole, specifically 30% by mole to 60% by mole, and y is 0% by mole to 70% by mole, specifically 0 mole percentage to 50 mole percentage, z is 0 mole percentage to 70 mole percentage, specifically 10 mole percentage to 50 mole percentage.

Further, the antireflection polymer has a weight average molecular weight of from 1,000 to 5,000, specifically from 2,000 to 4,000. If the weight average molecular weight of the antireflection polymer is too small, the yield is lowered when it is synthesized, so that the production cost becomes high, and if it is too large, the etch rate becomes slow, and gap filling is performed in the topology ( When gap-fill), a void can occur. The antireflection polymer may further contain other components in addition to Chemical Formula 1-1 to Chemical Formula 1-3.

The antireflection polymer may include the structure of the following Chemical Formula 3.

Chemical formula 3:

In Chemical Formula 3, R ₁ , R ₂ , R ₃ and R ₄ are the same as defined in Chemical Formula 1-1 to Chemical Formula 1-3, and x, y and z are used as moules constituting a repeating unit of the antireflection polymer. Percentage, x is 0 mole percentage to 70 mole percentage, specifically 30 mole percentage to 60 mole percentage, y is 0 mole percentage to 70 mole percentage, specifically 0 mole percentage to 50 mole percentage, z is from 0 mole percent to 70 mole percent, specifically from 10 mole percent to 50 mole percent. However, when the content of x is too small, film loss may occur, and if it is too large, the yield may decrease when the synthesis is performed, and if it is out of the content range of y, the antireflection function may be lowered (in the case of y) Next, as a spacer, in addition to the appropriate x, z content, it acts to fill the remaining portion). If it is out of the range of z, it is possible to reduce the antireflection function.

Typical examples of the polymer represented by Chemical Formula 3 include the following Chemical Formula 1a to Chemical Formula 1f. In the following Chemical Formula 1a to Chemical Formula 1f, x, y and z are the same as defined in Chemical Formula 3.

Chemical formula 1a:

Chemical formula 1b:

Chemical formula 1c:

Chemical formula 1d:

Chemical formula 1e:

Chemical formula 1f:

The isocyanurate compound has an excellent etching rate by containing a carbon-oxygen bond, and is represented by the following Chemical Formula 2.

Chemical formula 2:

In Chemical Formula 2, R is hydrogen or a methyl group, and R' may have one or more binding sites, each independently having a chain number of from 1 to 15 or a carbon number of from 3 to 6 hetero atoms. a ring-shaped saturated or unsaturated hydrocarbon group of 15 specifically, a chain having a carbon number of 1 to 8 or a ring having a carbon number of 3 to 8 containing 0 to 3 nitrogen (N) and/or oxygen (O) atoms a saturated or unsaturated hydrocarbon group, R", independently, a chain of 1 to 15 carbon atoms or a ring-shaped saturated or unsaturated hydrocarbon group having 3 to 15 carbon atoms containing 0 to 8 hetero atoms, R'' 'Independently, NH or O. R* are each independently S or O, and adjacent functional groups have the same element.

More specifically, R' is independently an alkyl group containing 0 to 2 hetero atoms, specifically, an alkyl group having an oxygen atom of 1 to 10, specifically, an alkyl group having 1 to 8 carbon atoms, respectively, R" respectively Independently comprising from 0 to 2 heteroatoms, in particular comprising from 1 to 10 carbon atoms, in particular from 1 to 6 carbon atoms or from 0 to 2 heteroatoms, comprising oxygen and/or sulfur atoms, Specifically, the carbon number containing oxygen and/or sulfur atoms is 4 to 10, specifically, a cycloalkyl group, an aryl group or a heterocyclic group having 5 to 6 carbon atoms.

A specific example of R' can be exemplified , , , , , , , , , , , , , , , , , , (where the curve ) indicates a binding site), and specific examples of R" may be exemplified , , , , , , (wherein, curve () indicates a binding site) and the like.

In the case where two or more binding sites of R' are present, the remaining portion of the isocyanurate compound represented by two or more chemical formulas 2 may be bonded to R' (for example, in isocyanide). In the case where the urethane compound is two or more, R' in one isocyanurate compound and R' in other isocyanurate compounds at other positions, etc.), whereby isocyanurate The compound may have a polymer structure.

The isocyanurate compound used in the present invention is reacted by using a compound containing two or more R's at a binding site, thereby using a compound formed into a polymer form or in the formation of an organic antireflection film. It is more effective to exist in the form of a polymer by crosslinking by a crosslinking agent. At this time, the isocyanurate compound has a weight average molecular weight (Mw) of from 2,000 to 10,000, specifically from 4,000 to 8,000. When the weight average molecular weight is too small, the organic antireflection film can be dissolved by the photocurable solvent. If it is too large, the solubility in a solvent is lowered, and the etching rate of the organic antireflection film may be lowered in the dry etching step.

Specific examples of the isocyanurate compound represented by Chemical Formula 2 include a compound containing a repeating unit represented by the following Chemical Formula 2a to Chemical Formula 2p.

Chemical formula 2a:

Chemical formula 2b:

Chemical formula 2c:

Chemical formula 2d:

Chemical formula 2e:

Chemical formula 2f:

Chemical formula 2g:

Chemical formula 2h:

Chemical formula 2i:

Chemical formula 2j:

Chemical formula 2k:

Chemical formula 2l:

Chemical formula 2m:

Chemical formula 2n:

Chemical formula 2o:

Chemical formula 2p:

The organic solvent may use a usual organic solvent for forming a composition of an organic antireflection film, for example, cyclohexanone, cyclopentanone, butyrolactone, dimethyl group may be used. Dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methyl pyrrolidone (NMP), tetrahydrofurfural alcohol, propylene glycol Propyleneglycol Monomethyl Ether (PGME), Propylene Glycol Monomethyl Ether Acetate (PGMEA), ethyl lactate (ethyl lactate), mixtures thereof, and the like, specifically, propylene glycol methyl ether acetate (PGMEA), An organic solvent such as propylene glycol monomethyl ether (PGME), cyclopentanone, or a mixture thereof.

In the composition for forming an organic anti-reflection film of the present invention, the antireflection polymer is contained in an amount of from 1% by weight to 10% by weight, specifically from 1% by weight to 5% by weight, more specifically from 2% by weight to 4% by weight The content by weight of the isocyanurate compound is from 1% by weight to 10% by weight, specifically from 1% by weight to 5% by weight, more specifically from 2% by weight to 4% by weight, and the solvent is from 85% by weight to 97.5% by weight Specifically, it is 88 weight% to 96.5 weight%, more specifically 89.35 weight% to 94.8 weight%. When the content of the isocyanurate compound is out of the range, the etching rate is low, and the efficiency may be lowered. If the content of the polymer is out of the range, problems may occur in the antireflection ability.

The composition for forming an organic anti-reflection film of the present invention may further comprise a crosslinking agent or an acid generator. The crosslinking agent forms a polymer by crosslinking a polymer compound and an isocyanurate compound, and can form an organic antireflection film. A usual crosslinking agent can be used, for example, melamine can be used. Crosslinking agent, etc.

The acid generator is used to promote the crosslinking reaction of the antireflection polymer compound and the isocyanurate compound, and a usual acid generator can be used. For example, an onium salt or an iodonium salt compound, a mixture thereof or the like can be used. Specifically, triphenylsulfonium nonaflate or dodecylbenzensulfonic acid can be used. ), paratoluenesulfonic acid, and the like. The content of the acid generator is 0.01% by weight to 0.5% by weight, specifically 0.05% by weight to 0.2% by weight, and if the content of the acid generating agent is less than 0.01% by weight, there is a possibility that there is no possibility of an organic antireflection film, if it is more than 0.5 Percent by weight, there is a concern that when the heating step is performed, fumes are generated to contaminate the device.

The content of the crosslinking agent is from 0.1% by weight to 1.5% by weight, specifically from 0.5 to 1% by weight, based on the total composition for forming the organic anti-reflection film of the present invention, and if the content of the crosslinking agent is too small, it is possible The organic anti-reflection film is not formed, and if it is too large, a footing or the like can be generated in the pattern outline.

The organic anti-reflection film of the present invention can be used for forming a composition for forming an organic anti-reflection film on the upper portion of an etched layer such as a ruthenium wafer or an aluminum substrate, and for coating an organic anti-reflection film. The composition is crosslinked to form a step. The step of applying the composition for forming the organic anti-reflection film may be carried out by a general method such as spin coating, roll coating, or the like, in the step of crosslinking the coated composition for forming the organic anti-reflection film, The coated composition can be heated in a device such as a high temperature plate, a convection oven or the like. Crosslinking is carried out at a temperature of from 90 ° C to 240 ° C, specifically at a temperature of from 150 ° C to 240 ° C. If the heating temperature is less than 90 ° C, there is insufficient removal of the remainder for forming an organic antireflection film. The solvent in the composition does not sufficiently carry out the crosslinking reaction. If the heating temperature is higher than 240 ° C, there is a fear that the composition for forming the organic antireflection film and the organic antireflection film become chemically unstable. .

When the organic anti-reflection film formed of the composition for forming an organic anti-reflection film of the present invention uses Cl ₂ /HBr/O ₂ , it can have an etching rate of 1.5 times or more of a common photoresist, and is used for dry etching. When the dry etching gas uses CFx, it may have an etching rate of 2.2 times or more. Specifically, the photoresist means a polyhydroxy-based photoresist.

The polymer 1 containing the chemical formula 1 can improve the anti-reflection and gap-filling properties, and has a high etching rate characteristic by including the polymer 2 of the chemical formula 2, and can be at a height. A scum-free organic anti-reflection film is formed in the difference region.

As shown in FIG. 1, the organic anti-reflection of the present invention is used instead of the SOC 22 or ACL 22 having a low etching rate and the oxide layer 21 with respect to the photoresist used between the existing photoresist 10 and the layer to be etched 30. The film 40 has a faster etching rate with respect to the photoresist, thereby reducing photoresist damage after etching, and is useful as a novel internal layer having an anti-reflection function, thereby simplifying the steps. Reduce costs, come to the economy, and solve the problem of scum on topology.

Moreover, the organic anti-reflection film of the present invention has an etching rate higher than that of the photoresist, so that as shown in FIG. 2, there is almost no difference in critical dimension (CD) 50 before and after the etching step, and vertical after etching. Outline.

Hereinafter, the present invention will be described in detail with reference to the embodiments, but the present invention is not limited to the following examples of the invention.

Preparation Example 1 to Preparation Example 6. Preparation of anti-reflection polymer

After the reactants 1 to 3 shown in the following Table 1 were placed in a 500 ml round bottom flask, methyl ethyl ketone (MEK) was added to dissolve the reactant 1 (hydroxy methacrylate). Hydroxyethyl methacrylate (HEMA), reactant 2 (Gamma-Butyrolactone (GBL) and Reactant 3 (see Table 1). Then, the temperature was raised to 80 using an oil bath. After the addition of 7.87 g of dimethyl 2,2'-Azobis (isobutyrate) (V-601) as an initiator, the reaction was carried out for 15 hours. After the completion of the reaction, the temperature was lowered. After normal temperature, the powder formed by heptane (Heptane) was filtered and dried to obtain a polymer (Preparation Example 1 to Preparation Example 6) (yield, weight average molecular weight (Mw), and polydispersity index (PDI) Refer to the following list 1).

Table 1

Preparation Example 7. Preparation of isocyanurate compounds

A-1. Preparation of isocyanurate compounds

Add 5 g of tris(1,3-oxathiane-2-thione-5-ylmethyl)isocyanurate (tris(1,3-oxathiolane-2-thion-5-ylmethyl) to the reactor. Isocyanurate) (0.0095 mol), 1.41 g of compound ( ) (0.0095 mol), 3.46 g of compound ( After (0.0285 mol) and 55.91 g of dimethylformamide (DMF), the mixture was stirred at room temperature (25 ° C) for 24 hours and reacted to prepare an isocyanuric acid represented by the following Chemical Formula 3 Ester compound (in the following Chemical Formula 4, R ₅ is or (Mohr ratio in total compound: : =1:3), at R ₅ In the case of the isocyanurate compound represented by the following Chemical Formula 3, except for the remaining two of R ₅ Connected to form a polymer. Yield: 85%, weight average molecular weight (Mw): 4905, polydispersity index (PDI): 1.83).

Chemical formula 4:

B-1. Preparation of Isocyanurate Compound represented by Chemical Formula 2h

To the reactor (250 ml round bottom flask), 76.29 g of tetrahydrofuran (THF) was added, and after 10 g of the compound represented by Chemical Formula 4 was dissolved, 5.01 g of triethylamine (TEA) was added, and an ice bath was used. Reduce the temperature to 0 °C. After 3.89 g of a compound (acetyl chloride) was slowly added dropwise to the solution, the reaction was carried out for 30 minutes, and the ice bath ice-bath was removed, and further reacted for 15 hours. After completion of the reaction, the solid was filtered, and the remaining solution was precipitated in diethyl ether, followed by filtration and drying to prepare an isocyanurate compound represented by Chemical Formula 2h (yield: 51, weight) Average molecular weight (Mw): 3000, polydispersity index (PDI): 1.32).

A-2. Preparation of isocyanurate compounds

5 g of 1,3,5-tris((2-oxa-1,3-dioxolan-4-yl)methyl)-1,3,5-triazine-2,4 was added to the reaction vessel. , 6-trione (0.0095 mmol), 1.41 g of compound ( ) (0.0095 mol), 3.46 g of compound ( After (0.0285 mol) and 55.91 g of dimethylformamide (DMF), the mixture was stirred at room temperature (25 ° C) for 24 hours and reacted to prepare an isocyanurate represented by the following Chemical Formula 3-2. Acid ester compound (in the following Chemical Formula 3-2, R ₅ is or (Mohr ratio in total compound: : =1:3), at R ₅ In the case of the isocyanurate compound represented by the following Chemical Formula 3-2, except for the remaining two of R ₅ The layers were joined to form a polymer (yield: 76%, weight average molecular weight (Mw): 4613, polydispersity index (PDI): 1.81).

Chemical formula 3-2:

To the reactor (250 ml round bottom flask), 76.29 g of tetrahydrofuran (THF) was added, and after 10 g of the isocyanurate compound represented by Chemical Formula 3-1 was dissolved, 5.01 g of triethylamine (triethylamine: TEA), and using an ice bath to reduce the temperature to 0 °C. After slowly adding 3.89 g of the compound (acetamidine chloride) to the solution, the reaction was carried out for 30 minutes, and after removing the ice-bath, the reaction was further carried out for 15 hours. After completion of the reaction, the solid was filtered, and the remaining solution was precipitated in diethyl ether, followed by filtration and drying to prepare an isocyanurate compound represented by Chemical Formula 3-2 (yield: 44) , weight average molecular weight (Mw): 2881, polydispersity index (PDI): 1.30).

Preparation of Compositions for Forming Organic Anti-Reflection Films of Examples 1 to 12 and Comparative Example 1

2% by weight of the polymer prepared in Preparation Examples 1 to 6 and 2% by weight of the isocyanide prepared in Preparation Example 7 were dissolved in 94.8 weight percent of propylene glycol methyl ether acetate (PGMEA) solvent. Urea compound A-1, 0.2% by weight of 2-Hydroxyhexyl p-toluenesulfonate as an acid generator and 1% by weight of Powderlink 1174 (tetramethoxy) as a crosslinking agent The composition for forming an organic anti-reflection film of Examples 1 to 6 was prepared by methylglycolide (1,3,4,6-Tetrakis(methoxymethyl)glycoluril). 4% by weight of Chemical Formula 1a, by dissolving 0.2% by weight of 2-hydroxyhexyl p-toluenesulfonate as an acid generator in 94.8 weight percent of propylene glycol methyl ether acetate (PGMEA) solvent And 1% by weight of Powderlink 1174 (1,3,4,6-Tetrakis (methoxymethyl)glycoluril) as a crosslinking agent to prepare the organic anti-composition of Comparative Example 1. A composition of a reflective film.

And, by dissolving 2% by weight of the polymer prepared in Preparation Example 1 to Preparation Example 2, respectively, in 24.8 wt% of propylene glycol methyl ether acetate solvent, 2% by weight of the isocyanuramide prepared in Preparation Example 7 Acid ester compound A-2, 0.2% by weight of 2-Hydroxyhexyl p-toluenesulfonate as an acid generator and 1% by weight of Powderlink 1174 (tetramethoxymethyl) as a crosslinking agent The composition for forming an organic anti-reflection film of Examples 7 to 12 was prepared by glycoluride.

Experimental Example 1 to Experimental Example 2. Dry etching (Cl ₂ /HBr/O ₂ , CFx) evaluation of organic anti-reflective coatings (bottom anti-reflective coating)

The organic anti-reflection film was spin-coated on the tantalum wafer at a composition of Examples 1 to 12 and Comparative Example 1, and then baked at 220 ° C / 60 seconds to form an organic anti-reflection film. For the organic anti-reflection film, Ram Research's electrolyte (Dielectric Etcher) (product name: Exelan HPT) was used as a dry etching gas, and Cl ₂ /HBr/O ₂ and CFx were used for etching for 10 seconds. The etching rate (nm/sec) of the organic anti-reflection film was determined by the thickness of the anti-reflection film before and after etching, and the results are shown in Table 2. The photoresist uses a polyhydroxy-based photoresist.

Table 2

Fig. 3 is a graph showing the etching rate of the photoresist and the organic antireflection film (bottom antireflection coating) of the present invention as a result of dry etching using Cl ₂ /HBr/O ₂ and CFx as dry etching gases, respectively. . When the etching step is performed, the usual anti-reflection film has a complicated step, so that it takes a long time to prepare a pattern, and the etching rate is slow with respect to the photoresist, so that when the etching step is performed, the photoresist is used. There is a limitation in the performing step, but it can be seen from Table 2 and FIG. 3 that the organic anti-reflection film of the present invention has a high etching rate with respect to the photoresist, and the etching step is reduced to reduce the etching. Damage to the photoresist. Therefore, the composition for forming an organic anti-reflection film of the present invention forms an effective organic anti-reflection film composition in a simplified aspect of the step by a fast etching rate. Also, the organic anti-reflection film formed of the composition for forming an organic anti-reflection film shows that when Cl ₂ /HBr/O ₂ is used as a dry etching gas, it has an etching rate of 1.5 times or more of the photoresist, when When CFx is used as the dry etching gas, the etching rate is 2.2 times or more. As in Comparative Example 1, when Cl ₂ /HBr/O ₂ is used as the dry etching gas, only the organic antireflection film and the light formed using the antireflection film polymer are used. The engraving has a slow etching rate, and when CFx is used as a dry etching gas, it has a faster etching rate than the photoresist, but is shown in comparison with the organic antireflection films of Embodiments 1 to 6. Slow etch rate.

10‧‧‧Photoresist

21‧‧‧Oxide or metal layer

22‧‧‧Spin carbon or amorphous carbon

30‧‧‧etched layer

40‧‧‧Anti-reflection film

50‧‧‧ critical size

Fig. 1 is a simplified view showing a procedure of an organic anti-reflection film of the present invention relating to a conventional organic anti-reflection film.

Fig. 2 is a view showing the difference in critical dimensions (CD) before and after the etch step.

Fig. 3 is a graph showing by comparing the etching rate of the photoresist and the organic anti-reflection film of the present invention.

Claims (16)

A composition for forming an organic anti-reflection film, comprising: an antireflection polymer comprising a repeating unit represented by the following Chemical Formula 1-1, Chemical Formula 1-2, and Chemical Formula 1-3; an isocyanurate compound , comprising more than one moiety represented by the following Chemical Formula 2; and an organic solvent, Chemical Formula 1-1: Chemical formula 1-2: Chemical formula 1-3: Chemical formula 2: In Chemical Formula 1-1 to Chemical Formula 1-3, R _{1 is} independently hydrogen or methyl, R ₂ is hydrogen or a hydrocarbon group having 1 to 5 carbon atoms containing 0 to 2 hetero atoms, and R ₃ is not included. a chromophore comprising from 0 to 2 heteroatoms having from 1 to 12 carbon atoms, and R ₄ being a chain or cyclic saturated or unsaturated hydrocarbon group having from 6 to 20 carbon atoms and containing from 0 to 2 hetero atoms. Is a hydrocarbyl group containing a chromophore, x is from 30 mole percent to 60 mole percent, y is from 0 mole percent to 50 mole percent, and z is from 10 mole percent to 50 mole percent, in Formula 2, R Is hydrogen or a methyl group, and R' is independently a chain having a carbon number of 1 to 15 containing 0 to 6 hetero atoms or a ring-shaped saturated or unsaturated hydrocarbon group having 3 to 15 carbon atoms, and R'' is contained. The heteroatoms of 0 to 8 have a chain number of 1 to 15 or a ring-shaped saturated or unsaturated hydrocarbon group of 3 to 15 carbon atoms, and R''' is independently NH or O, and R* is independently S or O, adjacent functional groups have the same elements. The composition for forming an organic anti-reflection film according to claim 1, wherein the anti-reflection polymer comprises the following Chemical Formula 3, Chemical Formula 3: In Chemical Formula 3, R ₁ , R ₂ , R ₃ and R ₄ are the same as defined in Chemical Formula 1-1 to Chemical Formula 1-3, and x, y, and z are the percentages of moles constituting the repeating unit of the polymer, x is from 30 mole percent to 60 mole percent, y is from 0 mole percent to 50 mole percent, and z is from 10 mole percent to 50 mole percent. The composition for forming an organic anti-reflection film according to claim 1, wherein the antireflection polymer is contained in an amount of from 1% by weight to 10% by weight. The composition for forming an organic anti-reflection film according to claim 1, wherein the isocyanurate compound is contained in an amount of from 1% by weight to 10% by weight. The composition for forming an organic anti-reflection film according to claim 1, wherein the composition for forming an organic anti-reflection film further comprises 0.1% by weight to 1.5% by weight for making isocyanuric acid A crosslinking agent crosslinked by an ester compound. The composition for forming an organic anti-reflection film according to claim 1, which further comprises 0.01 to 0.5% by weight of an acid generator for promoting a crosslinking reaction. The composition for forming an organic anti-reflection film according to claim 1, wherein R ₂ of Chemical Formula 1 is hydrogen or a hydrocarbon group having 1 to 3 carbon atoms and 0 to 2 hetero atoms, and R ₃ is A hydrocarbon group having 1 to 10 carbon atoms which does not contain a chromophore and contains 0 to 2 hetero atoms, and R ₄ contains a chromophore having 6 to 16 aryl groups as a 0 to 2 hetero atom. The composition for forming an organic anti-reflection film according to claim 1, wherein R' of the chemical formula 2 is independently a hydrocarbon group having 1 to 10 carbon atoms each containing 0 to 2 hetero atoms, R' 'Individually, respectively, a hydrocarbon group having 1 to 10 carbon atoms containing 0 to 2 hetero atoms or a cycloalkyl group, aryl group or heterocyclic group having 4 to 10 carbon atoms containing 0 to 2 hetero atoms. The composition for forming an organic anti-reflection film according to claim 1, wherein the antireflection polymer has a weight average molecular weight of from 1,000 to 5,000. The composition for forming an organic anti-reflection film according to claim 1, wherein the isocyanurate compound has a weight average molecular weight of from 2,000 to 10,000. The composition for forming an organic anti-reflection film according to claim 2, wherein the anti-reflection polymer is selected from the chemical formula 1a , chemical formula 1b , chemical formula 1c , chemical formula 1d , chemical formula 1e , chemical formula 1f And a mixture of its mixtures. The composition for forming an organic anti-reflection film according to claim 1, wherein the isocyanurate compound represented by Chemical Formula 2 is selected from Chemical Formula 2a , chemical formula 2b , chemical formula 2c , chemical formula 2d , chemical formula 2e , chemical formula 2f , chemical formula 2g , chemical formula 2h , chemical formula 2i , chemical formula 2j , chemical formula 2k , chemical formula 2l , chemical formula 2m , chemical formula 2n , chemical formula 2o , chemical formula 2p And a mixture of its mixtures. The composition for forming an organic anti-reflection film according to claim 1, wherein the organic solvent is selected from the group consisting of cyclohexanone, cyclopentanone, butyrolactone, dimethylacetamide, dimethyl An organic solvent in the group consisting of formamide, dimethyl hydrazine, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethyl lactate, and mixtures thereof. The composition for forming an organic anti-reflection film according to claim 1, wherein the organic anti-reflection film formed of the composition for forming an organic anti-reflection film has an etching rate higher than that of the photoresist. The composition for forming an organic anti-reflection film according to claim 1, wherein when Cl ₂ /HBr/O _{2 is} used as a dry etching gas, the composition for forming an organic anti-reflection film is formed. The organic anti-reflection film has an etching rate of 1.5 times or more of the photoresist. The composition for forming an organic anti-reflection film according to claim 1, wherein when CFx is used as the dry etching gas, the organic anti-reflection film formed of the composition for forming an organic anti-reflection film has The etching rate of the photoresist is 2.2 times or more.