KR20170086972A - Organic layer composition, and method of forming patterns - Google Patents

Abstract

Wherein the value of (D-peak B) / (D-peak K) and (G-peak B) / (G-peak K) are independently 5 or more, wherein the organic film composition . The definitions of (D-peak B), (D-peak K), (G-peak B), and (G-peak K) are as described in the specification.

Description

TECHNICAL FIELD The present invention relates to an organic film composition and a method of forming a pattern,

An organic film composition, and a pattern forming method using the organic film composition.

Recently, highly integrated design due to the miniaturization and complexity of electronic devices has accelerated the development of more advanced materials and related processes, so that lithography using existing photoresists also requires new patterning materials and techniques .

In the patterning process, an organic film called a hardmask layer, which is a hard interlayer, can be formed in order to transfer a fine pattern of photoresist to a substrate to a sufficient depth without collapse.

The hard mask layer acts as an interlayer to transfer the fine pattern of the photoresist to the material layer through the selective etching process. Therefore, the hard mask layer needs properties such as heat resistance and corrosion resistance to withstand the multiple etching process.

Meanwhile, it has recently been proposed that the hard mask layer is formed by a spin-on coating method instead of the chemical vapor deposition method. Generally, heat resistance and corrosion resistance are required to be compatible with spin-on characteristics, and an organic film material that can satisfy all of these properties.

One embodiment provides an organic film composition that can be applied to a spin-on coating system with good mechanical properties, corrosion resistance, heat resistance, chemical resistance, and good solubility characteristics.

Another embodiment provides a method of forming a pattern using the organic film composition.

(D-peak B) / (D-peak K) and (G-peak B) / (G-peak K) are independent from each other By weight based on the total weight of the composition.

The D-peak K is the intensity of the maximum absorption wavelength at 1350 cm ^-1 in the Raman spectra of the non-heat-treated thin film after coating the organic film composition with a thickness of 5000 Å, and the D-peak B is the intensity of the organic film composition And the G-peak K is the intensity of the maximum absorption wavelength at 1350 cm ^-1 in the Raman spectrum of the thin film formed by coating at a temperature of 300 to 600 ° C for 60 seconds to 180 seconds after coating the coating film with a thickness of 5,000 Å, and 1580 cm ^-1 in the Raman spectrum intensity at the maximum absorption wavelength of the non-heat-treated films was coated with a thickness 5000 Å, the G- peak B is from 300 to 600 ℃ after coating the composition the organic layer with a thickness 5000 Å Lt; ^-1 > cm < ^-1 > in the Raman spectrum of the thin film formed by heat treatment for 60 to 180 seconds.

The intensity (I _D ) of the maximum absorption wavelength at 1350 cm ^-1 in the Raman spectrum of the thin film formed by coating the organic film composition with a thickness of 5000 Å may be 500 or more and 300,000 or less.

The intensity (I _G ) of the maximum absorption wavelength at 1580 cm ^-1 in the Raman spectrum of the thin film formed by coating the organic film composition with a thickness of 5000 A may be 500 to 300,000.

The (D-peak B) / (D-peak K) and (G-peak B) / (G-peak K) values of the organic film composition may independently be 5 or more and 50 or less.

The organic polymer may have a weight average molecular weight of 300 to 20,000.

The organic polymer may comprise at least one substituted or unsubstituted benzene ring in its structural unit.

The organic polymer may include at least one substituted or unsubstituted polycyclic carbon ring within its structural unit.

The solvent may be selected from the group consisting of propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, N, N-dimethylformamide, N, N-dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone and ethyl 3-ethoxypropionate And may include at least one selected.

The organic polymer may be contained in an amount of 0.1% by weight to 50% by weight based on the total amount of the organic film composition.

The organic film composition may further include additives such as a surfactant, a crosslinking agent, a thermal acid generator, a plasticizer, or a combination thereof.

The crosslinking agent may be selected from the group consisting of methoxymethylated glycoluril, butoxymethylated glyceryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, Methoxymethylated thiourea, methoxymethylated benzene, butoxymethylated benzene, methoxymethylated phenol, butoxymethylated phenol, or a combination thereof.

According to another embodiment, there is provided a method of manufacturing a semiconductor device, comprising: providing a material layer on a substrate; applying the organic film composition on the material layer; heat treating the organic film composition to form a hard mask layer; Containing thin film layer; forming a photoresist layer on the silicon-containing thin film layer; exposing and developing the photoresist layer to form a photoresist pattern; Selectively removing the hard mask layer and exposing a portion of the material layer, and etching the exposed portion of the material layer.

The step of applying the organic film composition may be performed by a spin-on coating method.

The heat treatment may be performed at a temperature of 100 ° C to 600 ° C.

And forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist layer.

Provided is an organic film composition which has excellent mechanical properties, corrosion resistance, heat resistance and chemical resistance, and has good solubility characteristics and can be applied to a spin-on coating system.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the peak intensity according to the Raman variation of a pre-baked film formed from the hard mask composition according to Example 1,
2 to 6 are graphs showing the peak intensities of thin films formed from the hard mask composition according to Example 1 according to the Raman variation of the thin films baked at 200 ° C, 250 ° C, 300 ° C, 350 ° C and 400 ° C for 2 minutes, respectively Graph,
7 is a graph showing the peak intensity according to the Raman variation of the prebaked thin film formed from the hard mask composition according to Comparative Example 1,
8 to 12 are graphs showing the peak intensities of the thin films formed from the hard mask composition according to Comparative Example 1 according to the Raman variation of the thin films baked at 200 DEG C, 250 DEG C, 300 DEG C, 350 DEG C, and 400 DEG C for 2 minutes, respectively Graph,
13 is a graph showing the peak intensity according to the Raman variation of the prebaked thin film formed from the hard mask composition according to Example 2,
FIG. 14 is a graph showing the peak intensity of a thin film formed from the hard mask composition according to Example 2 according to the Raman variation of a thin film baked at 400 ° C for 2 minutes. FIG.

Hereinafter, exemplary embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Unless otherwise defined herein, 'substituted' means that a hydrogen atom in the compound is replaced by a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, A thio group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a cyano group, A C 1 to C 30 arylalkyl group, a C 7 to C 30 arylalkyl group, a C 1 to C 30 alkoxy group, a C 1 to C 20 heteroalkyl group, a C 2 to C 20 heteroaryl group, a C 3 to C 20 heteroarylalkyl group, a C 3 to C 30 cycloalkyl group, C3 to C15 monocyclic alkenyl groups, C6 to C15 cycloalkynyl groups, C2 to C30 heterocycloalkyl groups, and combinations thereof.

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

An organic film composition according to one embodiment will be described below.

The organic film composition according to an embodiment includes an organic polymer and a solvent. When the Raman spectrum is analyzed by forming a thin film according to a predetermined condition using the organic film composition, the organic film composition has a predetermined Raman characteristic.

When the intensity (I _D ) value of the maximum absorption wavelength at 1350 cm ^-1 in the Raman spectra is measured in the thin film state of the bake and in the thin film state after baking, the ratio of these measured values is a predetermined tendency I have.

Similarly, when the intensity (I _G ) value of the maximum absorption wavelength at 1580 cm ^-1 in the Raman spectra is measured in the thin film state of the bake and in the thin film state after baking, the ratio of these measured values is a predetermined It has a tendency.

The values of (D-peak B) / (D-peak K) and (G-peak B) / (G-peak K) of the organic film composition are independently 5 or more.

The D-peak K is an intensity of a maximum absorption wavelength at 1350 cm ^-1 in a Raman spectrum of a thin film which has not been heat-treated after coating the organic film composition with a thickness of 5000 Å, and the D- And the G-peak K is the intensity of the maximum absorption wavelength at 1350 cm ^-1 in the Raman spectrum of the thin film formed by coating at a temperature of 300 to 600 ° C for 60 seconds to 180 seconds after coating the coating film with a thickness of 5,000 Å, and 1580 cm ^-1 in the Raman spectrum intensity at the maximum absorption wavelength of the non-heat-treated films was coated with a thickness 5000 Å, the G- peak B is from 300 to 600 ℃ after coating the composition the organic layer with a thickness 5000 Å Means the intensity of the maximum absorption wavelength of 1580 cm ^-1 in the Raman spectrum of the thin film formed by heat treatment for 60 to 180 seconds.

In one example, the coating may be in accordance with a spin-on coating scheme.

The (D-peak B) / (D-peak K) value and the (G-peak B) / (G-peak K) value of the organic film composition come to this section due to the structure of the organic polymer.

The organic film composition according to one embodiment includes an organic polymer such that the value (D-peak B) / (D-peak K) and (G-peak B) / (G- peak K) , A thin film having excellent film strength and film density can be formed. In addition, the organic film composition has excellent solubility and can be applied to a spin-on coating method.

For example, the (D-peak B) / (D-peak K) value and the (G-peak B) / (G-peak K) value may independently be 5 or more and 50 or less, but are not limited thereto.

When the organic film composition is baked by a spin-on coating method, the organic film composition exhibits an sp ² characteristic peak in the range of 1000 cm ^-1 to 2000 cm ^-1 of the Raman spectrum.

For example, the organic film composition may have an intensity (I _D ) of 500 to 300,000 at a maximum absorption wavelength of 1350 cm ^-1 in a Raman spectrum of a thin film formed by coating the composition with a thickness of 5000 Å.

For example, the organic film composition may have a intensity (I _G ) at a maximum absorption wavelength of 1580 cm ^-1 of 500 to 300,000 in a Raman spectrum of a thin film formed by coating with a thickness of 5000 Å.

For example, the organic polymer included in the organic film composition may include at least one substituted or unsubstituted benzene ring in its structural unit, for example, the organic polymer may have at least one substituted or unsubstituted Or a polycyclic carbon ring.

For example, the organic polymer may have at least one substituted or unsubstituted aromatic ring group, a substituted or unsubstituted aliphatic ring group, a substituted or unsubstituted heteroaromatic ring group, a substituted or unsubstituted heteroaliphatic group, A cyclic group, or a combination thereof.

For example, the organic compound may include, but is not limited to, a monovalent or divalent organic group derived from a substituted or unsubstituted cyclic group selected from Group 1 below.

[Group 1]

The connecting point of the ring group selected in the group 1 is not particularly limited. The hydrogen in the ring group selected in the group 1 may be substituted with a substituent, and the kind and number of the substituent are not particularly limited.

For example, the organic polymer may have a weight average molecular weight of 300 to 20,000.

On the other hand, the solvent used in the organic film composition is not particularly limited as long as it has sufficient solubility or dispersibility to the organic polymer, and examples thereof include propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene glycol Propyleneglycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N, N-dimethylformamide, N, N (trimethylolpropane) - at least one selected from dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone and ethyl 3-ethoxypropionate.

The organic polymer may be included in an amount of about 0.1 to 50 wt%, or about 0.1 to 30 wt%, based on the total amount of the organic film composition. By including the organic polymer in the above range, the thickness, surface roughness and planarization degree of the organic film can be controlled.

The organic film composition may further include additives such as a surfactant, a crosslinking agent, a thermal acid generator, and a plasticizer.

The surfactant may be, for example, an alkylbenzenesulfonate, an alkylpyridinium salt, a polyethylene glycol, or a quaternary ammonium salt, but is not limited thereto.

Examples of the cross-linking agent include melamine-based, substitution-based, or polymer-based ones. Preferably, the crosslinking agent having at least two crosslinking substituents is, for example, a methoxymethylated glyceryl, butoxymethylated glyceryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxy Methylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea and the like can be used.

As the crosslinking agent, a crosslinking agent having high heat resistance can be used. As the crosslinking agent having a high heat resistance, a compound containing a crosslinking forming substituent group having an aromatic ring (for example, a benzene ring or a naphthalene ring) in the molecule can be used.

The acid generator may be an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid or naphthalenecarboxylic acid and / , 4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters, but are not limited thereto.

The additive may be included in an amount of about 0.001 to 40 parts by weight based on 100 parts by weight of the organic film composition. By including it in the above range, the solubility can be improved without changing the optical properties of the organic film composition.

According to another embodiment, there is provided an organic film produced using the organic film composition described above. The organic layer may be in the form of a hardened layer, for example, a hard mask layer, a planarization layer, a sacrificial layer, a filler, etc., and an organic thin film used for electronic devices, .

Hereinafter, a method of forming a pattern using the organic film composition described above will be described.

The method of forming a pattern according to one embodiment includes the steps of providing a material layer on a substrate, applying the above-described organic film composition on the material layer, heat treating the organic film composition to form a hard mask layer, Forming a silicon-containing thin film layer on the silicon-containing thin film layer, forming a photoresist layer on the silicon-containing thin film layer, exposing and developing the photoresist layer to form a photoresist pattern, Selectively removing the thin film layer and the hard mask layer and exposing a portion of the material layer, and etching the exposed portion of the material layer.

The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate.

The material layer is a material to be finally patterned and may be a metal layer such as aluminum, copper, or the like, a semiconductor layer such as silicon, or an insulating layer such as silicon oxide, silicon nitride, or the like. The material layer may be formed by, for example, a chemical vapor deposition method.

The organic film composition is as described above, and may be prepared in a solution form and applied by a spin-on coating method. At this time, the coating thickness of the organic film composition is not particularly limited, but may be applied to a thickness of about 50 to 10,000 ANGSTROM.

The heat treatment of the organic film composition may be performed at about 100 to 500 DEG C for about 10 seconds to 1 hour.

The silicon-containing thin film layer may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, SiO and / or SiN.

Further, a bottom anti-reflective coating (BARC) may be further formed on the silicon-containing thin film layer before the step of forming the photoresist layer.

The step of exposing the photoresist layer may be performed using, for example, ArF, KrF or EUV. Further, after the exposure, a heat treatment process may be performed at about 100 to 600 ° C, for example, 300 to 600 ° C.

The step of etching the exposed portion of the material layer may be performed by dry etching using an etching gas, and the etching gas may be, for example, CHF ₃ , CF ₄ , Cl ₂ , BCl ₃ and a mixed gas thereof.

The etched material layer may be formed in a plurality of patterns, and the plurality of patterns may be a metal pattern, a semiconductor pattern, an insulation pattern, or the like, and may be applied to various patterns in a semiconductor integrated circuit device, for example.

Hereinafter, embodiments of the present invention will be described in detail with reference to examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Synthetic example

Comparative Synthetic Example  One

(21.6 g, 0.057 mol) and 9.6 g (0.057 mol) of 1,4-bis (methoxymethyl) benzene were added to a 500 ml flask equipped with a thermometer, a condenser and a mechanical stirrer. and 0.15 g (0.001 mol) of diethylsulfite were added thereto, followed by stirring at 90 to 120 ° C for about 5 to 10 hours. Samples were taken from the polymerization reactants at intervals of 1 hour, and the reaction was completed when the weight average molecular weight of the sample was 1,800 to 2,300.

After completion of the polymerization reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into 40 g of distilled water and 400 g of methanol, stirred vigorously, and allowed to stand. The supernatant was removed and the precipitate was dissolved in 80 g of PGMEA (PGMEA), and then 40 g of metalol and 40 g of water were stirred vigorously (1 st). The resulting supernatant was again removed and the precipitate was dissolved in 40 g of propylene glycol monomethyl ether acetate (PGMEA) (second order). The primary and secondary processes were referred to as a one-time purification process, and this purification process was performed three times in total. The purified polymer was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA), and methanol and distilled water remaining in the solution were then removed under reduced pressure to obtain a polymer (Mw: 2,500).

Synthetic example  One

The flask was charged with 1H-inodole (13.3 g, 0.1 mol), 2-hydroxyperylene-3-carboxaldehyde (29.6.0 g, 0.1 mol), p-Toluenesulfonic acid monohydrate (9.5 g, 60 g) was added thereto, followed by stirring at 100 占 폚. Samples were taken from the polymerization reactants at intervals of 1 hour, and the reaction was completed when the weight average molecular weight of the sample was 3,000 to 4,000. After completion of the reaction, 100 g of hexane was added to extract 1,4-dioxane. Methanol was added thereto, and the resulting precipitate was filtered, and the remaining monomer was removed using methanol to obtain a polymer (Mw: 3,500).

Synthetic example  2

(33.2 g, 0.2 mol), 1-methoxynaphthalene (15.8 g, 0.1 mol) and propylene glycol monomethyl ether acetate (PGMEA) (72.2 g) were added to a solution of 4-methoxypyrene , And 0.62 g (4 mmol) of diethylsulfate were polymerized in the same manner as in Comparative Synthesis Example 1 to give a polymer (Mw: 2,500).

Example : Hard mask  Preparation of composition

Example  One

The polymer obtained in Synthesis Example 1 was dissolved in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7: 3 (v / v)) and then filtered to obtain a hard mask composition . The content of the polymer was controlled according to the thickness of the desired thin film.

Example  2

A hard mask composition was prepared in the same manner as in Example 1, except that the polymer obtained in Synthesis Example 2 was used in place of the polymer obtained in Synthesis Example 1.

Comparative Example  One

A hard mask composition was prepared in the same manner as in Example 1 except that the polymer obtained in Comparative Synthesis Example 1 was used in place of the polymer obtained in Synthesis Example 1

evaluation

Evaluation 1-1: Identification of Raman spectra of thin films (1)

On the silicon wafer, the hard mask composition according to Examples 1 and 2 and Comparative Example 1 was spin-on coated to a thickness of 5,000 Å and baked on a hot plate to form a thin film. The baking was carried out at different temperatures, i.e. 200 ° C., 250 ° C., 300 ° C., 350 ° C. and 400 ° C. for 2 minutes each.

The formed thin film was measured for Raman spectrum according to the following condition 1.

[Condition 1]

Analytical equipment: Invia (Renishaw); 785 nm-laser (Grating 1200 l / min)

Exposure time: 10 sec

Measurement area: 100 cm ^-1 to 4000 cm ^-1

On the other hand, after spin-coating the hard mask composition according to Examples 1 and 2 and Comparative Example 1 to a thickness of 5,000 Å, the Raman spectrum of the thin film was measured in the same manner as in the condition 1 before the baking.

A graph of the peak intensity according to the Raman shift obtained by processing the measurement result is shown in Figs.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the peak intensity according to the Raman variation of a pre-baked film formed from the hard mask composition according to Example 1,

2 to 6 are graphs showing the peak intensities of thin films formed from the hard mask composition according to Example 1 according to the Raman variation of the thin films baked at 200 ° C, 250 ° C, 300 ° C, 350 ° C and 400 ° C for 2 minutes, respectively Graph,

7 is a graph showing the peak intensity according to the Raman variation of the prebaked thin film formed from the hard mask composition according to Comparative Example 1,

8 to 12 are graphs showing the peak intensities of the thin films formed from the hard mask composition according to Comparative Example 1 according to the Raman variation of the thin films baked at 200 DEG C, 250 DEG C, 300 DEG C, 350 DEG C, and 400 DEG C for 2 minutes, respectively Graph,

13 is a graph showing the peak intensity according to the Raman variation of the prebaked thin film formed from the hard mask composition according to Example 2,

FIG. 14 is a graph showing the peak intensity of a thin film formed from the hard mask composition according to Example 2 according to the Raman variation of a thin film baked at 400 ° C for 2 minutes. FIG.

Referring to FIGS. 1 to 12, a thin film formed from the hard mask composition according to Example 1 has a D-peak and a G peak during baking at temperatures of 300 DEG C, 350 DEG C, and 400 DEG C, It can be seen that the D-peak and the G peak are not observed in all of the thin films formed from the mask composition in the whole temperature range.

6, the thin film formed by baking at 400 ° C for 2 minutes using the hard mask composition according to Example 1 had an intensity ( _ID ) of 300,000 at a maximum absorption wavelength of 1350 cm ^-1 in a Raman spectrum , And the intensity (I _G ) at the maximum absorption wavelength of 1580 cm ^-1 is 300,000.

14, the thin film formed by baking at 400 DEG C for 2 minutes using the composition from the hard mask composition according to Example 2 had an intensity (I _D ) of the maximum absorption wavelength at 1350 cm ^-1 in the Raman spectrum 300,000, and the intensity (I _D ) of the maximum absorption wavelength at 1580 cm ^-1 is 300,000.

Evaluation 1-2: Identification of Raman spectra of thin films (2)

(D-peak B) / (D-peak K) and (G-peak B) of the thin film formed from the hard mask composition according to Examples 1 and 2 and Comparative Example 1 from the Raman spectrum results obtained in Evaluation 1-1, / (G-peak K) was calculated.

The results are shown in Table 1 below.

Bake temperature Example 1 Example 2 Comparative Example 1 (D-peak B) /
(D-peak K) (G-peak B) /
(G-peak K) (D-peak B) /
(D-peak K) (G-peak B) /
(G-peak K) (D-peak B) / (D-peak K) (G-peak B) / (G-peak K) 300 ° C 7.2 10.0 (Not measured) (Not measured) 1.1 1.3 350 ℃ 9.9 12.7 (Not measured) (Not measured) 1.2 1.2 400 ° C 10.6 13.8 10.9 14.3 1.1 1.4

(D-peak B) / (D-peak K) means (D peak intensity after baking) / (D peak intensity before baking) ) Means (G peak intensity after baking) / (G peak intensity before baking).

Referring to Table 1 above, the thin films formed from the hard mask compositions according to Examples 1 and 2 were different from the thin films formed from the hard mask composition according to Comparative Example 1 (D-peak B) / (D-peak K) and (G - peak B) / (G-peak K) all have a value of 5 or more.

Evaluation 2: Thin film strength

The hard mask composition according to Examples 1 and 2 and Comparative Example 1 was spin-on coated on a silicon wafer at 1,000 Å on a silicon wafer and heat treated at 400 ° C. for 2 minutes on a hot plate to measure the thickness of the thin film. The film density was then measured using XRD.

The results are shown in Table 2.

Film density (g / cm ³ ) Example 1 1.41 Example 2 1.39 Comparative Example 1 1.25

Referring to Table 2, it can be seen that the thin film formed from the hard mask composition according to Examples 1 and 2 has excellent film density characteristics as compared with the thin film formed from the hard mask composition according to Comparative Example 1. [

Evaluation 3: Thin film strength

The hard mask composition according to Examples 1 and 2 and Comparative Example 1 was spin-on coated on a silicon wafer to a thickness of 5,000 Å and heat treated at 400 ° C for 2 minutes on a hot plate to form a thin film. Then, the hardness / modulus ratio (H / E) of the thin film was measured by measuring the hardness (H) and the modulus (E) of the thin film using a nanoindenter (cube corner tip, P _max = 300 μN).

The results are shown in Table 3.

H (GPa) E (GPa) H / E Example 1 0.9 11 0.082 Example 2 0.8 11 0.073 Comparative Example 1 0.6 17 0.035

Referring to Table 3, the thin film formed from the hard mask composition according to Examples 1 and 2 has a relatively large hardness / modulus ratio (H / E) as compared with the thin film formed from the hard mask composition according to Comparative Example 1 It can be seen that it has excellent film strength characteristics.

Rating 4: Etch rate

On the silicon wafer, the hard mask composition according to Examples 1 and 2 and Comparative Example 1 was spin-on coated to a thickness of 4,000 Å and heat treated at 400 ° C for 2 minutes on a hot plate to form a thin film, and then the thickness of the thin film was measured. Subsequently, the thin film was dry-etched using a mixed gas of CHF ₃ / CF _{4 and a} mixed gas of N ₂ / O _2, and then the thickness of the thin film was measured again.

The bulk etch rate (BER) was calculated from the thickness and etch time of the thin film before and after dry etching according to the following equation.

[Equation 1]

Bulk etch rate (BER) = (initial thin film thickness - thin film thickness after etching) / etching time (Å / sec)

The results are shown in Table 4.

The etching rate (Å / sec) CHF ₃ / CF ₄ mixed gas N ₂ / O ₂ mixed gas Example 1 25 22 Example 2 26 23 Comparative Example 1 28 26

Referring to Table 4, the thin films formed from the hard mask compositions according to Examples 1 and 2 were compared with the films formed from the hard mask composition according to Comparative Example 1 in a mixed gas of CHF ₃ / CF ₄ and N ₂ / O ₂ It is understood that the etching rate is relatively small and the etching resistance is excellent.

Evaluation 5: Pattern profile

A 3,000 Å thick silicon oxide (SiO ₂ ) layer was formed on the silicon wafer by a chemical vapor deposition method. Next, 13.0 wt% of the hard mask composition according to Examples 1 and 2 and Comparative Example 1 was coated on the silicon oxide layer by a spin-on coating method, and then heat-treated at 400 ° C for 2 minutes on a hot plate to form a hard mask layer Respectively.

A silicon nitride (SiN) layer was formed on the hard mask layer by a chemical vapor deposition method. Subsequently, the photoresist for KrF was coated and heat-treated at 110 ° C. for 60 seconds, exposed using ASML (XT: 1400, NA 0.93) exposure equipment, and developed with tetramethylammonium hydroxide (2.38 wt% TMAH aqueous solution).

Subsequently, the silicon nitride layer was dry-etched using a mixed gas of CHF ₃ / CF ₄ using the patterned photoresist as a mask. Then, the hard mask layer was dry-etched using a N ₂ / O ₂ mixed gas using the patterned silicon nitride layer as a mask. Then, the silicon oxide layer was dry-etched using a CHF ₃ / CF ₄ mixed gas using the patterned hard mask layer as a mask, and then the remaining organic substances were removed using O ₂ gas.

Sectional view of the hard mask layer and the silicon oxide layer pattern was observed using an electron microscope (SEM).

The results are shown in Table 5.

Hard mask layer
Pattern shape Silicon oxide layer
Pattern shape Example 1 Vertical Vertical Example 2 Vertical Vertical Comparative Example 1 Tapered Tapered

Referring to Table 5, the hard mask layer formed from the hard mask composition according to Examples 1 and 2 and the silicon oxide layer below it were all patterned in a vertical shape, while the hard mask layer formed from the hard mask composition according to Comparative Example 1 It can be seen that the layer is not patterned in a vertical shape but is patterned in a tapered shape.

From this, it can be seen that the thin film formed from the hard mask composition according to Examples 1 and 2 is formed in a good pattern with excellent film strength as compared with the thin film formed from the hard mask composition according to Comparative Example 1, It can be seen that the material layer is also formed in a good pattern.

Evaluation 6: Optical properties (n, k-value)

On the silicon wafer, the hard mask composition according to Examples 1 and 2 and Comparative Example 1 was spin-on coated to a thickness of 1,000 Å and heat treated at 400 ° C. for 2 minutes on a hot plate to form a thin film. Then, using an Ellipsometer (JA Woollam) The refractive index (n) and the extinction coefficient (k) of the thin film were measured.

The results are shown in Table 6.

193 nm 633 nm n k n K Example 1
1.41 0.52
1.89 0.28 Example 2 1.43 0.52
1.80 0.25 Comparative Example 1 1.45 0.58 1.69 0.01

Referring to Table 1, it can be seen that the hard mask compositions according to Examples 1 to 3 have refractive indices and absorptions usable as antireflection films at 193 nm and 633 nm wavelengths.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.

Claims (15)

Organic polymers, and
menstruum
Wherein the organic film composition comprises:
(D-peak B) / (D-peak K) and (G-peak B) / (G-peak K)
The D-peak K is the intensity of the maximum absorption wavelength at 1350 cm ^-1 in the Raman spectrum of the thin film without coating after coating the organic film composition with a thickness of 5000 Å,
The D-peak B is the intensity of the maximum absorption wavelength of 1350 cm ^-1 in the Raman spectrum of the thin film formed by coating the organic film composition with a thickness of 5000 Å and then heat-treating the film at 300 to 600 ° C. for 60 to 180 seconds,
The G-peak K is the intensity of the maximum absorption wavelength of 1580 cm- ¹ in the Raman spectrum of the thin film without coating after coating the organic film composition with a thickness of 5000 angstroms,
The G-peak B is the intensity at a maximum absorption wavelength of 1580 cm ^-1 in a Raman spectrum of a thin film formed by coating the organic film composition with a thickness of 5000 Å and heat-treating it at 300 to 600 ° C. for 60 to 180 seconds. The method of claim 1,
Wherein an intensity (I _D ) of a maximum absorption wavelength at 1350 cm ^-1 in an Raman spectrum of a thin film formed by coating the organic film composition with a thickness of 5000 Å is 500 to 300,000. The method of claim 1,
Wherein the intensity (I _G ) of the maximum absorption wavelength at 1580 cm ^-1 in the Raman spectrum of the thin film formed by coating the organic film composition with a thickness of 5000 A is 500 to 300,000. The method of claim 1,
Wherein the values of (D-peak B) / (D-peak K) and (G-peak B) / (G- peak K) are independently 5 or more and 50 or less. The method of claim 1,
Wherein the organic polymer has a weight average molecular weight of 300 to 20,000. The method of claim 1,
Wherein the organic polymer comprises at least one substituted or unsubstituted benzene ring in its structural unit. 8. The method of claim 7,
Wherein the organic polymer comprises at least one substituted or unsubstituted polycyclic carbon ring in its structural unit. The method of claim 1,
The solvent may be selected from the group consisting of propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, N, N-dimethylformamide, N, N-dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone and ethyl 3-ethoxypropionate And at least one selected from the group consisting of silicon oxide and silicon nitride. The method of claim 1,
Wherein the organic polymer is contained in an amount of 0.1% by weight to 50% by weight based on the total amount of the organic film composition. The method of claim 1,
Wherein the organic film composition further comprises an additive for a surfactant, a crosslinking agent, a thermal acid generator, a plasticizer, or a combination thereof. 11. The method of claim 10,
The crosslinking agent may be selected from the group consisting of methoxymethylated glycoluril, butoxymethylated glyceryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, A methoxymethylated thioether, a methoxymethylated benzene, a butoxymethylated benzene, a methoxymethylated phenol, a butoxymethylated phenol, or a combination thereof. Providing a layer of material over the substrate,
Applying the organic film composition according to any one of claims 1 to 11 to the material layer,
Heat treating the organic film composition to form a hard mask layer,
Forming a silicon-containing thin film layer on the hard mask layer,
Forming a photoresist layer on the silicon-containing thin film layer,
Exposing and developing the photoresist layer to form a photoresist pattern
Selectively removing the silicon-containing thin film layer and the hard mask layer using the photoresist pattern and exposing a portion of the material layer, and
Etching the exposed portion of the material layer
≪ / RTI > The method of claim 12,
Wherein the step of applying the organic film composition is performed by a spin-on coating method. The method of claim 12,
Wherein the heat treatment is performed at a temperature of 100 ° C to 600 ° C. The method of claim 12,
Further comprising forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist layer.

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