Monomer, hardmask composition comprising monomer, and pattern forming method using hardmask composition

Abstract

Disclosed are a monomer for a hardmask composition represented by the following Chemical Formula 1, a hardmask composition including the monomer, and a method of forming patterns using the hardmask composition. ##STR00001## In the above Chemical Formula 1, A, A′ , X, Y, I, m and n are the same as described in the detailed description.

Claims

1. A monomer for a hardmask composition, the monomer being represented by the following Chemical Formula 1: ##STR00012## wherein, in the above Chemical Formula 1, A is a substituted or unsubstituted polycyclic aromatic group, A′ is a substituted or unsubstituted C6 to C20 arylene group, X is an epoxy-containing group, Y is a hydroxy group, a C1 to C10 alkylamine group, —NH.sub.2, ═O, or a combination thereof, I is an integer of 0 to 6, and m and n are each independently an integer of 1 to 4.

2. The monomer of claim 1, wherein A is a substituted or unsubstituted one of the following polycyclic aromatic groups: ##STR00013##

3. The monomer of claim 1, wherein A′ is the substituted C6 to C20 arylene group, the substituted C6 to C20 arylene group being substituted with a hydroxy group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C10 alkylamine group, or a combination thereof.

4. The monomer of claim 1, wherein the monomer is represented by one of the following Chemical Formulae 2 to 5: ##STR00014## wherein, in the above Chemical Formulae 2 to 5, n is an integer of 1 to 4.

5. The monomer of claim 1, wherein the monomer has a molecular weight of 200 to 5,000.

6. A hard mask composition, comprising: a monomer represented by the following Chemical Formula 1, and a solvent: ##STR00015## wherein, in the above Chemical Formula 1, A is a substituted or unsubstituted polycyclic aromatic group, A′ is a substituted. or unsubstituted C6 to C20 arylene group, X is an epoxy-containing group, Y is a hydroxy group, a C1 to C10 alkylamine group, —NH.sub.2, ═O, or a combination thereof, I is an integer of 0 to 6, and m and n are each independently an integer of 1 to 4.

7. The hardmask composition of claim 6, wherein A is a substituted or unsubstituted one of the following polycyclic aromatic groups. ##STR00016##

8. The hardmask composition of claim 6, wherein A′ is the substituted C6 to C20 arylene group, the substituted C6 to C20 arylene group being substituted with a hydroxy group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C10 alkylamine group, or a combination thereof.

9. The hardmask composition of claim 6, wherein the monomer is represented by one of the following Chemical Formulae 2 to 5: ##STR00017## wherein, in the above Chemical Formulae 2 to 5, n is an integer of 1 to 4.

10. The hardmask composition of claim 6, wherein the monomer has a molecular weight of 200 to 5000.

11. The hardmask composition of claim 6, wherein the monomer is included in the composition in an amount of 0.1 to 50 wt %, based on a total weight of the hardmask composition.

12. A method of forming patterns, the method comprising: providing a material layer on a substrate, applying a hardmask composition on the material layer, heat-treating the hardmask composition to form a hardmask layer, forming a silicon-containing thin layer on the hardmask layer, forming a photoresist layer on the silicon-containing thin layer, exposing and developing the photoresist layer to form a photoresist pattern selectively removing the silicon-containing thin layer and the hardmask layer using the photoresist pattern to expose a part of the material layer, and etching an exposed part of the material layer, wherein the hardmask composition includes; a monomer represented by the following Chemical Formula 1, and a solvent: ##STR00018## wherein, in the above Chemical Formula 1, A is a substituted or unsubstituted polycyclic aromatic group, A′ is a substituted. or unsubstituted C6 to C20 arylene group, X is an epoxy-containing group, Y is hydrogen, a hydroxy group, a C1 to C10 alkylamine group, —NH.sub.2, ═O, or a combination thereof, I is an integer of 0 to 6, and m and n are each independently an integer of 1 to 4.

13. The method of claim 12, wherein applying the hardmask composition includes performing a spin-on coating method.

14. The method of claim 12, wherein heat-treating the hardmask layer is performed at 100° C. to 500° C.

15. The method of claim 12, wherein A is a substituted or unsubstituted one of the following polycyclic aromatic groups: ##STR00019##

16. The method of claim 12, wherein A′ is the substituted C6 to C20 arylene group, the substituted C6 to C20 arylene group being substituted with a hydroxy group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C10 alkylamine group, or a combination thereof.

17. The method of claim 12, wherein the monomer is represented by one of the following Chemical Formulae 2 to 5: ##STR00020## wherein, in the above Chemical Formulae 2 to 5, n is an integer of 1 to 4.

18. The method of claim 12, wherein the monomer has a molecular weight of 200 to 5000.

19. The method of claim 12, wherein the monomer is included in the composition in an amount of 0.1 to 50 wt %, based on a total weight of the hardmask composition.

20. A monomer for a hardmask composition, the monomer being represented by the following Chemical Formula 1: ##STR00021## wherein, in the above Chemical Formula 1, A is a substituted or unsubstituted polycyclic aromatic group, A′ is a substituted C6 to C20 arylene group, the substituted C6 to C20 arylene group being substituted with a hydroxy group, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C10 alkylamine group, or a combination thereof, X is an epoxy-containing group, Y is a hydrogen, a hydroxy group, a C1 to C10 alkylamine group, NH2, ═O, or a combination thereof, I is an integer of 0 to 6, and m and n are each independently an integer of 1 to 4.

Description

Mode for Invention

(1) Hereinafter, the present disclosure is illustrated in more detail with reference to examples. However, these examples are exemplary, and the present disclosure is not limited thereto.

Synthesis of Monomer

Synthesis Example 1

(2) 2.86 g (0.01 mol) of 2,7-di(oxiran-2-yl)pyrene and 5.72 g (0.03 mol) of 2-naphthoyl chloride, and 50 ml of dichloroethane were put in a 100 ml flask under a nitrogen atmosphere and agitated for 1 hour, and 2.93 g (0.022 mol) of AlCl.sub.3 was slowly added thereto. The mixture was agitated at room temperature. Then, 50 ml of deionized water was added, completing the reaction (12 hr, RT) after confirming if the starting materials were all removed through gel permeation chromatography (GPC). 50 ml of ethyl acetate was used to extract an organic layer, and the organic layer was twice rinsed with 30 ml of deionized water and concentrated under a reduced pressure, obtaining a compound represented by the following Chemical Formula 6.

(3) ##STR00008##

(4) The yield of the compound was 81%, and the compound had an average molecular weight of 510.

Synthesis Example 2

(5) 3.36 g (0.01 mol) of 2,7-di(oxiran-2-yl)pyrene, 4.68 g (0.03 mol) of 4-hydroxy benzoyl chloride, and 50 ml of dichloroethane were put in a 100 ml flask and agitated for 1 hour, and 4.39 g (0.033 mol) of AlCl.sub.3 was slowly added thereto. The mixture was agitated at room temperature. 50 ml of deionized water was added to the resultant, completing the reaction (18 hr, RT) after confirming if the starting materials were all removed through gel permeation chromatography (GPC). 50 ml of ethyl acetate was used to extract an organic layer, and the organic layer were twice rinsed with 30 ml of deionized water and concentrated under a reduced pressure, obtaining a compound represented by the following Chemical Formula 7.

(6) ##STR00009##

(7) The yield of the compound was 72%, and the compound had an average molecular weight of 565.

Comparative Synthesis Example 1

(8) A compound represented by the following Chemical Formula 8 was synthesized according to the same method as Synthesis Example 1 except for using pyrene as a starting material.

(9) ##STR00010##

(10) The yield of the compound was 68%, and the compound had an average molecular weight of 470.

Comparative Synthesis Example 2

(11) A compound represented by the following Chemical Formula 9 was synthesized according to the same method as Synthesis Example 2 except for using perylene as a starting material.

(12) ##STR00011##

(13) The yield of the compound was 79%, and the compound had an average molecular weight of 553.

Preparation of Hardmask Composition

Example 1

(14) 1 g of the compound according to Synthesis Example 1 was completely dissolved in 9 g of propylene glycol monomethyl ether acetate (PGMEA), preparing a hardmask composition.

Example 2

(15) 1 g of the compound according to Synthesis Example 2 was completely dissolved in 9 g of propylene glycol monomethyl ether acetate (PGMEA), preparing a hardmask composition.

Comparative Example 1

(16) 1g of the compound according to Comparative Synthesis Example 1 was completely dissolved in 9 g of propylene glycol monomethyl ether acetate (PGMEA), preparing a hardmask composition.

Comparative Example 2

(17) 1 g of the compound according to Comparative Synthesis Example 2 was completely dissolved in 9 g of propylene glycol monomethyl ether acetate (PGMEA), preparing a hardmask composition.

Evaluation

Evaluation 1: Out-Gas Evaluation

(18) The hardmask compositions according to Examples 1 and 2 and Comparative Examples 1 and 2 were respectively spin-on coated on a silicon wafer, forming about 2,000 Å-thick thin films. The films were baked at 180° C. for 120 seconds, and out-gas produced during the baking was measured using QCM (Quartz Crystal Microbalance).

(19) The out-gas evaluation results are provided in Table 1.

(20) TABLE-US-00001 TABLE 1 Out-gas (ng/100 Å) Example 1 1.7 Example 2 1.6 Comparative Example 1 2.4 Comparative Example 2 2.1

(21) Referring to Table 1, the hardmask compositions according to Examples 1 and 2 showed less amount of out-gas than the hardmask compositions according to Comparative Examples 1 and 2 at the same temperature of 180° C.

(22) The reason is that the hardmask compositions according to Examples 1 and 2 had excellent cross-linking compared with the hardmask compositions according to Comparative Examples 1 and 2, and accordingly, the hardmask compositions according to Examples 1 and 2 might be stably baked.

Evaluation 2: Evaluation of Etching Resistance

(23) The hardmask compositions according to Examples 1 and 2 and Comparative Examples 1 and 2 were spin-on coated on a silicon wafer and heat-treated on a hot plate at 240° C. and 400° C. for 120 seconds, forming each thin film. Then, thicknesses of the thin films were measured using a measuring device made by K-MAC.

(24) The thin films were dry-etched for 60 seconds by using N.sub.2/O.sub.2 mixed gas, and the thicknesses of the thin films were measured. In addition, the thin films were dry-etched for 100 seconds by using CF.sub.x gas, and thicknesses of the thin films were measured.

(25) The thicknesses of the thin films before and after the dry etching and etching time were used to calculate a bulk etch rate (BER) according to the following Calculation Equation 1.

(26) [Calculation Equation 1]

(27) (Initial thin film thickness—thin film thickness after etching)/etching time (Å/s)

(28) The results are provided in Table 2.

(29) TABLE-US-00002 TABLE 2 Etch rate(Å/s) N.sub.2/O.sub.2 CF.sub.X 240° C. 400° C. 240° C. 400° C. Example 1 22.08 18.71 24.54 26.17 Example 2 21.24 17.36 23.22 26.20 Comparative Example 1 24.72 22.35 27.07 30.33 Comparative Example 2 23.57 22.21 26.94 29.12

(30) Referring to Table 2, the thin films formed of the hardmask compositions according Examples 1 and 2 showed sufficient etching resistance for etching gas compared with the hardmask compositions according to Comparative Examples 1 and 2 and thus, a low etch rate.

(31) While this invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.