HIGHLY THICK SPIN-ON-CARBON HARD MASK COMPOSITION AND PATTERNING METHOD USING SAME

Abstract

Proposed is a composition for a thick hard mask suitable for use in a semiconductor lithography process, and particularly a spin-on carbon hard mask composition and a patterning method of forming a hard mask layer by applying the composition on an etching target layer through spin coating and baking the composition. The composition has high solubility characteristics, thereby enabling the formation of a thick hard mask which can exhibit high etching resistance to tolerate multiple etching processes and excellent mechanical properties.

Claims

1. A spin-on carbon hard mask composition comprising: a polymer having a weight average molecular weight of 2,000 to 200,000, and having a structure represented Chemical Formula 1: ##STR00017## In Chemical Formula 1, l, m, and n are 1≤l≤40, 1≤m≤40, and 1≤n≤40, respectively, R.sub.1 comprises any one selected from among hydrogen (H), a hydroxyl group (OH), ##STR00018## R.sub.2 comprises any one selected from among, ##STR00019## and R.sub.3 comprises any one selected from among ##STR00020##

2. The spin-on carbon hard mask composition of claim 1, wherein, in R.sub.1 in Chemical Formula 1, X.sub.1 to X.sub.35 each independently comprise hydrogen, a hydroxyl group, a substituted or unsubstituted C.sub.1 to C.sub.3 alkyl group, or a combination thereof.

3. The spin-on carbon hard mask composition of claim 1, wherein the weight average molecular weight of the polymer is in a range of 2,500 to 20,000.

4. The spin-on carbon hard mask composition of claim 3, wherein the weight average molecular weight of the polymer is in a range of 3,500 to 15,000.

5. The spin-on carbon hard mask composition of claim 1, wherein the spin-on hard mask composition comprises the polymer represented by Chemical Formula 1, an organic solvent, and a surfactant.

6. The spin-on carbon hard mask composition of claim 5, wherein the polymer is contained in an amount of 1% to 50% by weight based on a total amount of the composition.

7. The spin-on carbon hard mask composition of claim 5, wherein the organic solvent is contained in an amount of 50% to 99% by weight based on a total amount of the composition.

8. The spin-on carbon hard mask composition of claim 5, wherein the surfactant is contained in an amount of 0% to 2% by weight based on a total amount of the composition.

9. The spin-on carbon hard mask composition of claim 5, wherein the organic solvent is one or a mixture of at least two selected from the group consisting of propylene glycol monomethylether (PGME), propylene glycol monomethylether acetate (PGMEA), cyclohexanone, γ-butyrolactone, ethyl lactate (EL), methyl ethyl ketone, n-butyl acetate, N-methylpyrrolidone (NMP), methyl 3-methoxypropionate (MMP), ethyl 3-ethoxypropionate (EEP), and dimethylformamide (DMF).

10. The spin-on carbon hard mask composition of claim 5, wherein the surfactant is one or a mixture of at least two selected from the group consisting of polyoxyethylene alkylethers, polyoxyethylene alkylphenylethers, polyoxyethylene nonylphenylethers, polyoxyethylene octylphenylethers, polyoxyethylene polyoxypropylenes, polyoxyethylene lauryl ethers, and polyoxyethylene sorbitans.

11. The spin-on carbon hard mask composition of claim 5, wherein the spin-on hard mask composition comprises 1% to 50% by weight of the polymer, 50% to 99% by weight of the organic solvent, and 0% to 2% by weight of the surfactant.

12. The spin-on carbon hard mask composition of claim 11, wherein the organic solvent is one or a mixture of at least two selected from the group consisting of propylene glycol monomethylether (PGME), propylene glycol monomethylether acetate (PGMEA), cyclohexanone, γ-butyrolactone, ethyl lactate (EL), methyl ethyl ketone, n-butyl acetate, N-methylpyrrolidone (NMP), methyl 3-methoxypropionate (MMP), ethyl 3-ethoxypropionate (EEP), and dimethylformamide (DMF).

13. The spin-on carbon hard mask composition of claim 11, wherein the surfactant is one or a mixture of at least two selected from the group consisting of polyoxyethylene alkylethers, polyoxyethylene alkylphenylethers, polyoxyethylene nonylphenylethers, polyoxyethylene octylphenylethers, polyoxyethylene polyoxypropylenes, polyoxyethylene lauryl ethers, and polyoxyethylene sorbitans.

14. A patterning method comprising forming a hard mask layer by: applying the spin-on hard mask composition of claim 1 on an etching target layer through spin coating; and baking the composition.

15. The patterning method of claim 14, wherein the baking is performed at a temperature of 150° C. to 400° C. for 1 to 5 minutes, thereby forming the hard mask layer.

Description

DESCRIPTION OF DRAWINGS

[0023] FIG. 1 is an .sup.1H-NMR spectrum of a polymer prepared in Example 1.

BEST MODE

[0024] Hereinafter, a detailed description will be given of the present disclosure.

[0025] One aspect of the present disclosure pertains to a spin-on carbon hard mask composition having a structure represented by Chemical Formula 1, and having a weight average molecular weight of 2,000 to 200,000, preferably 2,500 to 20,000, and more preferably 3,500 to 15,000.

##STR00005##

[0026] In Chemical Formula 1, l, m, and n are 1≤l≤40, 1≤m≤40, and 1≤n≤40, respectively,

[0027] R.sub.1 includes any one selected from among hydrogen (H), a hydroxyl group (OH),

##STR00006##

[0028] R.sub.2 includes any one selected from among,

##STR00007##

[0029] and R.sub.3 includes any one selected from among

##STR00008##

[0030] In R.sub.1 in Chemical Formula 1, X.sub.1 to X.sub.35 each independently include hydrogen, a hydroxyl group, a substituted or unsubstituted C.sub.1 to C.sub.3 alkyl group, or a combination thereof.

[0031] In Chemical Formula 1, R.sub.2 is mainly used under an acid catalyst condition and plays the role of increasing the solubility of a formed polymer in an organic solvent.

[0032] In Chemical Formula 1, R.sub.3 mainly plays the role of improving the thermosetting reactivity and etching selectivity of the entire polymer structure.

[0033] The polymer represented by Chemical Formula 1 has a weight average molecular weight of 2,000 to 200,000, preferably 2,500 to 20,000, and more preferably 3,500 to 15,000.

[0034] When the weight average molecular weight of the polymer represented by Chemical Formula 1 is less than 2,500, a sufficient amount of the polymer structure is not formed, thereby lowering etching resistance. On the other hand, when the weight average molecular weight thereof exceeds 20,000, the properties of the coated surface may become non-uniform.

[0035] The hard mask composition may include 1% to 50% by weight of the polymer represented by Chemical Formula 1, 50% to 99% by weight of an organic solvent, and 0% to 2% by weight of a surfactant.

[0036] When the amount of the polymer is less than 1% by weight or exceeds 50% by weight, the coating thickness may be less than or exceeds a desired level, making it difficult to obtain an exact coating thickness. An excessive coating thickness may result in deteriorated coatability.

[0037] The organic solvent may be one or a mixture of at least two selected from the group consisting of propylene glycol monomethylether (PGME), propylene glycol monomethylether acetate (PGMEA), cyclohexanone, γ-butyrolactone, ethyl lactate (EL), methyl ethyl ketone, n-butyl acetate, N-methylpyrrolidone (NMP), methyl 3-methoxypropionate (MMP), ethyl 3-ethoxypropionate (EEP), and dimethylformamide (DMF).

[0038] The surfactant may be one or a mixture of at least two selected from the group consisting of nonionic surfactants, such as polyoxyethylene alkylethers, polyoxyethylene alkylphenylethers, polyoxyethylene nonylphenylethers, polyoxyethylene octylphenylethers, polyoxyethylene polyoxypropylenes, polyoxyethylene lauryl ethers, and polyoxyethylene sorbitans.

[0039] The surfactant may function to lower surface tension, thereby increasing spreadability or permeability to thereby contribute to an improvement in coatability or gap-filling performance.

[0040] Another aspect of the present disclosure pertains to a patterning method, including forming a hard mask layer by applying the composition on an etching target layer through spin coating and baking the composition.

[0041] The spin coating thickness of the composition may be in the range of from 100 Å to 30,000 Å, but is not is not particularly limited thereto.

[0042] The baking may be performed at a temperature of 150° C. to 400° C. for 1 to 5 minutes. During the baking process, the composition may undergo a self-crosslinking reaction.

[0043] Hereinafter, preferred Examples and Comparative Examples of the present disclosure will be described below. However, the following Examples are only examples of the present disclosure, and the present disclosure is not limited thereto.

MODE FOR INVENTION

Example 1

[0044] ##STR00009##

[0045] 18 g of 1-hydroxypyrene, 9.5 g of 1,4-bismethoxymethylbenzene, 20 g of 9,9-bis(6-hydroxy-2-naphthyl)fluorene, and 150 g of propylene glycol monomethylether acetate (PGMEA) were mixed, and a nitrogen atmosphere was created. Then, 0.20 g of diethyl sulfate was added thereto, and the resulting solution was heated to 140° C. and then refluxed for 18 hours. After termination of the reaction, the resulting solution was purified with a hexane/methanol/water (1:1:1) solution, recrystallized using a methanol/water (10:1) solution, and dried in a vacuum, thereby obtaining a polymer compound having a weight average molecular weight (Mw) of 10,500, as measured by GPC based on standard polystyrene.

Example 2

[0046] ##STR00010##

[0047] A polymer compound was synthesized in the same manner as in Example 1, except that the resulting solution was heated to 140° C. and then refluxed for 6 hours. The weight average molecular weight (Mw) of the polymer compound thus obtained was 1,900 as measured by GPC based on standard polystyrene.

Example 3

[0048] ##STR00011##

[0049] A polymer compound was synthesized in the same manner as in Example 1, except that 0.40 g of diethyl sulfate was added thereto, and the resulting solution was heated to 140° C. and then refluxed for 36 hours. The weight average molecular weight (Mw) of the polymer compound thus obtained was 25,000 as measured by GPC based on standard polystyrene.

Example 4

[0050] ##STR00012##

[0051] A polymer compound was synthesized in the same manner as in Example 1, except that 25 g of 3-hydroxyperylene was added in lieu of 1-hydroxypyrene. The weight average molecular weight (Mw) of the polymer compound thus obtained was 9,500 as measured by GPC based on standard polystyrene.

Example 5

[0052] ##STR00013##

[0053] A polymer compound was synthesized in the same manner as in Example 1, except that 23 g of 1-anthrol was added in lieu of 1-hydroxypyrene. The weight average molecular weight (Mw) of the polymer compound thus obtained was 8,500 as measured by GPC based on standard polystyrene.

Example 6

[0054] ##STR00014##

[0055] A polymer compound was synthesized in the same manner as in Example 1, except that 19 g of 2-naphthol was added in lieu of 1-hydroxypyrene. The weight average molecular weight (Mw) of the polymer compound thus obtained was 7,500 as measured by GPC based on standard polystyrene.

Comparative Example 1

[0056] ##STR00015##

[0057] 20 g of 9,9-bis(4-hydroxyphenyl)fluorene and 9.5 g of 1,4-bismethoxymethylbenzene were added with 70 g of PGMEA, after which 0.20 g of diethyl sulfate was added thereto. Then, the same synthesis procedure as in Example 1 was performed, thereby obtaining a polymer compound, the weight average molecular weight (Mw) of which was 9,000 as measured by GPC based on standard polystyrene.

Comparative Example 2

[0058] The same synthesis procedure as in Comparative Example 1 was performed, except that the reaction time was set to 6 hr, to obtain a polymer compound. The weight average molecular weight (Mw) of the polymer compound thus obtained was 1,800 as measured by GPC based on standard polystyrene.

Comparative Example 3

[0059] ##STR00016##

[0060] 22 g of 9,9-bis(6-hydroxy-2-naphthyl)fluorene and 9.5 g of 1,4-bismethoxymethylbenzene were added with 150 g of PGMEA, after which 0.20 g of diethyl sulfate was added thereto. Then, the same synthesis procedure as in Example 1 was performed, thereby obtaining a polymer compound, the weight average molecular weight (Mw) of which was 9,700 as measured by GPC based on standard polystyrene.

Test Example 1

[0061] 3.0 g of the polymer compound obtained in Example 1, 37.6 g of propylene glycol monomethylether acetate, and 9.7 g of cyclohexanone were added and stirred for 20 hours until dissolving. The resulting solution was filtered through a 0.2-μm microfilter, thus preparing a composition for forming a hard mask layer, which was then applied on a silicon wafer using a spin coater. The coated wafer was heated on a hot plate using the sequence of 240° C. for 1 minute and 400° C. for 1 minute, thereby forming a hard mask layer.

Test Example 2

[0062] The same procedure as in Test Example 1 was performed, except that 3.0 g of the polymer compound obtained in Example 2 was used.

Test Example 3

[0063] The same procedure as in Test Example 1 was performed, except that 3.0 g of the polymer compound obtained in Example 3 was used.

Test Example 4

[0064] The same procedure as in Test Example 1 was performed, except that 3.0 g of the polymer compound obtained in Example 4 was used.

Test Example 5

[0065] The same procedure as in Test Example 1 was performed, except that 3.0 g of the polymer compound obtained in Example 5 was used.

Test Example 6

[0066] The same procedure as in Test Example 1 was performed, except that 3.0 g of the polymer compound obtained in Example 6 was used.

Test Example 7

[0067] The same procedure as in Test Example 1 was performed, except that 17.0 g of the polymer compound obtained in Example 1, 26.4 g of propylene glycol monomethylether acetate, and 6.6 g of cyclohexanone were used.

Test Example 8

[0068] The same procedure as in Test Example 7 was performed, except that 17.0 g of the polymer compound obtained in Example 2 was used.

Test Example 9

[0069] The same procedure as in Test Example 7 was performed, except that 17.0 g of the polymer compound obtained in Example 3 was used.

Test Example 10

[0070] The same procedure as in Test Example 7 was performed, except that 17.0 g of the polymer compound obtained in Example 4 was used.

Test Example 11

[0071] The same procedure as in Test Example 7 was performed, except that 17.0 g of the polymer compound obtained in Example 5 was used.

Test Example 12

[0072] The same procedure as in Test Example 7 was performed, except that 17.0 g of the polymer compound obtained in Example 6 was used.

[0073] Comparative Test Example 1

[0074] The same procedure as in Test Example 1 was performed, except that 3.0 g of the polymer compound obtained in Comparative Example 1 was used.

Comparative Test Example 2

[0075] The same procedure as in Test Example 1 was performed, except that 3.0 g of the polymer compound obtained in Comparative Example 2 was used.

Comparative Test Example 3

[0076] The same procedure as in Test Example 1 was performed, except that 3.0 g of the polymer compound obtained in Comparative Example 3 was used.

Comparative Test Example 4

[0077] The same procedure as in Test Example 7 was performed, except that 17.0 g of the polymer compound obtained in Comparative Example 1 was used.

Comparative Test Example 5

[0078] The same procedure as in Test Example 7 was performed, except that 17.0 g of the polymer compound obtained in Comparative Example 2 was used.

Comparative Test Example 6

[0079] The same procedure as in Test Example 7 was performed, except that 17.0 g of the polymer compound obtained in Comparative Example 3 was used.

[0080] <Measurement of Weight Average Molecular Weight>

[0081] The weight average molecular weight of the polymer of each of Examples was measured through gel permeation chromatography (GPC). The measurement was performed using a GPC device made by WATERS, and the measurement conditions were as follows.

[0082] Column temperature: 40° C., mobile phase: tetrahydrofuran (THF), flow rate: 1 mL/1 min, GPC column: STYRAGEL KF-801, 802, 803 (made by WATERS, 8×300 mm).

[0083] <Test of Coating Thickness>

[0084] The thickness of the hard mask layer formed in each of Test Examples 1 to 12 and Comparative Test Examples 1 to 6 was measured. The results are illustrated in Table 1 below. The measurement was performed using an ellipsometer (Horiba).

TABLE-US-00001 TABLE 1 Coating Sample thickness (nm) Coatability Test Example 1  Example 1 150 Good Test Example 2  Example 2 110 Good Test Example 3  Example 3 230 Good Test Example 4  Example 4 160 Good Test Example 5  Example 5 145 Good Test Example 6  Example 6 140 Good Test Example 7  Example 1 2800 Good Test Example 8  Example 2 2200 Good Test Example 9  Example 3 3040 Poor Test Example 10 Example 4 2870 Good Test Example 11 Example 5 2650 Good Test Example 12 Example 6 2520 Good Comparative Comparative 130 Good Test Example 1 Example 1 Comparative Comparative 100 Good Test Example 2 Example 2 Comparative Comparative 139 Good Test Example 3 Example 3 Comparative Comparative 2380 Poor Test Example 4 Example 1 Comparative Comparative 1850 Poor Test Example 5 Example 2 Comparative Comparative 2450 Poor Test Example 6 Example 3

[0085] <Test of Optical Properties> The refractive index n and extinction coefficient k of the hard mask layer formed in each of Test Examples 1 to 12 and Comparative Test Examples 1 to 6 were measured. The results are illustrated in Table 2 below. The measurement was performed using an ellipsometer (Horiba).

TABLE-US-00002 TABLE 2 Refractive Extinction index coefficient Sample (n@193 nm) (k@193 nm) Test Example 1  Example 1 1.40 0.46 Test Example 2  Example 2 1.39 0.46 Test Example 3  Example 3 1.40 0.47 Test Example 4  Example 4 1.43 0.48 Test Example 5  Example 5 1.50 0.50 Test Example 6  Example 6 1.53 0.51 Test Example 7  Example 1 1.40 0.46 Test Example 8  Example 2 1.39 0.46 Test Example 9  Example 3 — — Test Example 10 Example 4 1.43 0.48 Test Example 11 Example 5 1.50 0.50 Test Example 12 Example 6 1.53 0.51 Comparative Comparative 1.44 0.69 Test Example 1 Example 1 Comparative Comparative 1.44 0.69 Test Example 2 Example 2 Comparative Comparative 1.38 0.48 Test Example 3 Example 3 Comparative Comparative — — Test Example 4 Example 1 Comparative Comparative — — Test Example 5 Example 2 Comparative Comparative — — Test Example 6 Example 3

[0086] The refractive induces n and extinction coefficients k of the hard mask layer were measured as shown in Table 2 above, except for those formed in Test Example 9 and Comparative Test Examples 4 to 6, which were not measured due to poor coatability.

[0087] <Evaluation of Dry-Etching Characteristics> The hard mask layers formed in Test Examples 1 to 12 and Comparative Test Examples 1 to 6 were subjected to dry etching for 20 seconds using CF4 gas by means of a dry-etching device. The dry-etching rate was defined as [(film thickness before dry etching-film thickness after dry etching)/time]. The dry-etching characteristics refer to a dry-etching rate of a hard mark film when the dry-etching rate of an amorphous carbon layer (ACL) is taken as 100%, and the cross-section of each hard mask layer was observed using a field emission scanning electron microscope (FE-SEM, Hitachi). The results are illustrated in Table 3 below.

TABLE-US-00003 TABLE 3 CF4 etching characteristics Sample compared to ACL Test Example 1  Example 1 92.0% Test Example 2  Example 2 88.0% Test Example 3  Example 3 93.0% Test Example 4  Example 4 93.5% Test Example 5  Example 5 91.0% Test Example 6  Example 6 90.0% Test Example 7  Example 1 92.0% Test Example 8  Example 2 88.0% Test Example 9  Example 3 92.8% Test Example 10 Example 4 93.3% Test Example 11 Example 5 90.6% Test Example 12 Example 6 90.3% Comparative Test Comparative 81.0% Example 1 Example 1 Comparative Test Comparative 56.4% Example 2 Example 2 Comparative Test Comparative 84.0% Example 3 Example 3 Comparative Test Comparative — Example 4 Example 1 Comparative Test Comparative — Example 5 Example 2 Comparative Test Comparative — Example 6 Example 3 ACL  100%

[0088] A hard mask layer with excellent etching resistance means that the dry etching rate of the hard mask layer is about 90% of the dry etching rate of an amorphous carbon layer. The results of Test Examples 1 to 12 and Comparative Test Examples 1 to 6 revealed that the dry etching rate was about 90%, meaning excellent etching resistance. Although the present disclosure has been described in detail with reference to the specific features, it will be apparent to those skilled in the art that this description is only for a preferred embodiment and does not limit the scope of the present disclosure. Thus, the substantial scope of the present disclosure will be defined by the appended claims and equivalents thereof.