CN108427246B - Composition for hard mask - Google Patents
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- CN108427246B CN108427246B CN201810130569.8A CN201810130569A CN108427246B CN 108427246 B CN108427246 B CN 108427246B CN 201810130569 A CN201810130569 A CN 201810130569A CN 108427246 B CN108427246 B CN 108427246B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
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- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
The inventionDisclosed is a composition for a hard mask, which is capable of forming a hard mask having improved flatness, solubility and etching resistance at the same time by using a polymer comprising an aromatic compound having 6-35 carbon atoms and a compound of the following chemical formula 1, and a solvent. In the following chemical formula 1, R1And R2Each independently is an alkyl group having 1 to 8 carbon atoms, and may be linked to each other to form a ring, the alkyl group may further contain one or more oxygen atoms in the main chain, and Ar is a functional group derived from an aromatic compound having 6 to 20 carbon atoms.
Description
Technical Field
The present invention relates to a composition for a hard mask.
Background
For example, in the fields of semiconductor manufacturing, microelectronics, and the like, the degree of integration of structures such as circuits, wirings, and insulating patterns is continuously increasing. Therefore, photolithography processes for fine patterning of the above-described structures have also been developed.
In general, a photoresist layer is formed by coating a photoresist on a film to be etched, and a photoresist pattern is formed by exposure and development processes. Next, the film to be etched is partially removed using the photoresist pattern as an etching mask, so that a predetermined pattern can be formed. After the image transfer to the film to be etched, the photoresist pattern may be removed by ashing (ashing) and/or stripping (strip).
In order to suppress the decrease in resolution due to light reflection in the exposure step, an anti-reflective coating (ARC) layer may be formed between the film to be etched and the photoresist layer. In this case, since the ARC layer is additionally etched, the consumption amount or etching amount of the photoresist layer or the photoresist pattern may increase. In addition, when the thickness of the film to be etched is increased or the amount of etching required for forming a desired pattern is increased, sufficient etching resistance of the photoresist layer or the photoresist pattern may not be secured.
Therefore, in order to secure etching resistance and etching selectivity of a photoresist for forming a desired pattern, a resist lower film may be added between the film to be etched and the photoresist layer.
The resist lower film needs to have sufficient etching resistance (etching resistance) and heat resistance for a high-temperature etching process, for example, and also needs to be formed in a uniform thickness by a spin coating process, for example.
Korean laid-open patent No. 10-2010-0082844 discloses an example of a resist lower film-forming composition.
Documents of the prior art
Patent document
Korean laid-open patent No. 10-2010-0082844
Disclosure of Invention
Problems to be solved
An object of the present invention is to provide a composition for a hard mask, which can form a hard mask having excellent etching resistance, solubility and flatness.
Means for solving the problems
1. A composition for a hard mask, comprising a polymer of an aromatic compound having 6 to 35 carbon atoms and a compound of the following chemical formula 1, and a solvent:
[ chemical formula 1]
(in chemical formula 1, R is as defined above)1And R2Each independently an alkyl group having 1 to 8 carbon atoms, which may be bonded to each other to form a ring, the above-mentioned alkylThe group may further contain one or more oxygen atoms in the main chain, and the Ar is a functional group derived from an aromatic compound having 6 to 20 carbon atoms).
2. The composition for a hard mask according to claim 1, wherein the Ar of the chemical formula 1 comprises at least one selected from the group consisting of the following chemical formulae Ar-1 to Ar-4:
[ chemical formula Ar-1]
[ chemical formula Ar-2]
[ chemical formula Ar-3]
[ chemical formula Ar-4]
3. The composition for a hard mask as set forth in claim 1, wherein the compound of the above chemical formula 1 comprises at least one selected from the group consisting of the following chemical formulas 1-1 to 1-5:
[ chemical formula 1-1]
[ chemical formulas 1-2]
[ chemical formulas 1-3]
[ chemical formulas 1 to 4]
[ chemical formulas 1 to 5]
(wherein Ar is a functional group derived from an aromatic compound having 6 to 20 carbon atoms).
4. The composition for a hard mask as described in claim 1, wherein the aromatic compound having 6 to 35 carbon atoms comprises at least one compound selected from the group consisting of the following chemical formulas 2-1 to 2-6:
[ chemical formula 2-1]
[ chemical formula 2-2]
[ chemical formulas 2-3]
[ chemical formulas 2-4]
[ chemical formulas 2 to 5]
[ chemical formulas 2 to 6]
(wherein R is as defined above3One or more of the above aromatic compounds may be used, and each is independently hydrogen or a hydroxyl group).
5. The composition for a hard mask according to claim 1, wherein the polymer comprises a repeating unit of the following chemical formula 3:
[ chemical formula 3]
(in chemical formula 3, Ar is as defined above1Ar is a group derived from the aromatic compound having 6 to 35 carbon atoms, which may be further substituted with a hydroxyl group2Derived from the compound of the above chemical formula 1, n is an integer of 1 to 200).
6. The composition for a hard mask as set forth in claim 1, the above polymer being represented by the following chemical formula 3-1:
[ chemical formula 3-1]
(in the above chemical formula 3-1, Ar is described above1Ar is a functional group derived from the aromatic compound having 6 to 35 carbon atoms, Ar is independently a functional group derived from the aromatic compound having 6 to 20 carbon atoms, and R is4And R5Each independently represents a methyl group or an ethyl group, n1 is an integer of 1 to 200, and n2 is 0 or 1).
7. The composition for a hard mask as described in claim 5, wherein the polymer consists of Ar only1And Ar2And (4) forming.
8. The composition for a hard mask as set forth in claim 1, further comprising at least one of a crosslinking agent, a catalyst and a surfactant.
Effects of the invention
By using the composition for a hard mask of the embodiment of the present invention, a hard mask having excellent flatness and simultaneously improved etching resistance, heat resistance and solubility can be formed.
The composition for a hard mask according to an embodiment of the present invention may include a polymer produced using an aromatic compound having 6 to 35 carbon atoms and a compound containing 2 or more ether groups. Due to the rotational characteristics of the ether group, the flexibility of the polymer is increased, and the flatness of the hard mask film can be improved.
In addition, the composition for a hard mask according to an embodiment of the present invention includes a polymer having a structure derived from an aromatic compound having a high carbon content, thereby improving heat resistance and etching resistance.
Further, by using a hard mask formed from the composition for a hard mask, a high-resolution photolithography process can be realized, and a desired target pattern with a desired fine line width can be formed.
Detailed Description
An embodiment of the present invention provides a composition for a hard mask, which includes a polymer of an aromatic compound having 6 to 35 carbon atoms and a compound of the following chemical formula 1, and a solvent:
[ chemical formula 1]
(in chemical formula 1, R is as defined above)1And R2Independently an alkyl group having 1 to 8 carbon atoms, which may be linked to each other to form a ring, the alkyl group may further contain one or more oxygen atoms in the main chain, and Ar is a functional group derived from an aromatic compound having 6 to 20 carbon atoms).
The present invention can provide a composition for a hard mask, which is excellent in flatness, heat resistance, etching resistance and solubility, by including the above polymer.
The composition for a hard mask may be applied between a photoresist layer and a film to be etched to form a hard mask film serving as a resist underlayer film, for example. The hard mask film may be partially removed by the photoresist pattern to form a hard mask, and the hard mask may be used as an additional etching mask.
The above-described hard mask film or hard mask can be used, for example, as a Spin-On hard mask (Spin-On Hardmask: SOH).
Hereinafter, the composition for a hard mask according to the embodiment of the present invention will be described in detail. In the case where the compound or resin represented by the chemical formula used in the present application has isomers, the compound or resin represented by the chemical formula means a representative chemical formula including the isomers thereof.
The composition for a hard mask according to an embodiment of the present invention includes a polymer of an aromatic compound having 6 to 35 carbon atoms and a compound of the above chemical formula 1, a solvent, and may further include an additional agent such as a crosslinking agent and a catalyst.
Polymers of aromatic compounds
According to an embodiment of the present invention, the composition for a hard mask may include a polymer of an aromatic compound formed by condensation polymerization of an aromatic compound having 6 to 35 carbon atoms and a compound of the chemical formula 1.
The polymer according to an embodiment of the present invention includes the compound of the above chemical formula 1 as a linker.
The Ar in the chemical formula 1 is a functional group derived from an aromatic compound having 6 to 20 carbon atoms, and may include at least one selected from the group consisting of the following chemical formulas Ar-1 to Ar-4:
[ chemical formula Ar-1]
[ chemical formula Ar-2]
[ chemical formula Ar-3]
[ chemical formula Ar-4]
The polymer according to an embodiment of the present invention may form a linear (linear) structure having stable energy by including a structure derived from the compound of chemical formula 1, thereby improving etching resistance against plasma energy. The reason why the etching resistance is improved is because the above-mentioned linear structure is less hindered (steric hindrance) and relatively stable in energy compared to the branched (branched) structure, and the linear polymer has a higher bulk density (packing density) compared to the branched (branched) polymer. It is judged that the polymer of this example can have the above-mentioned linear structure because the reactivity (electrophilic substitution reactivity) of the compound of the above chemical formula 1 is low and the selectivity is improved according to the "reactivity-selectivity rule". On the other hand, in the case of using a linker such as an aldehyde compound which is not an example of the present invention, the structure of the polymerized polymer shows a high tendency of a non-linear branched polymer (branched polymer), and the energy of the polymer is unstable and the etching resistance is relatively lowered.
In addition, the polymer according to an embodiment of the present invention includes an ether group in the polymer, and the polymer has increased flexibility due to the rotational characteristics of the ether group, so that the flatness of the hard mask film can be improved, and the polymer may include an alkoxy group at the end instead of a hydrogen atom or a hydroxyl group, which can generate a relatively strong attractive force such as a hydrogen bond, so that the viscosity of the composition may be reduced and the solubility may be improved.
For example, the compound of the above chemical formula 1 may include at least one selected from the group consisting of the following chemical formulas 1-1 to 1-5:
[ chemical formula 1-1]
[ chemical formulas 1-2]
[ chemical formulas 1-3]
[ chemical formulas 1 to 4]
[ chemical formulas 1 to 5]
(wherein Ar is a functional group derived from an aromatic compound having 6 to 20 carbon atoms),
specifically, at least one selected from the group consisting of chemical formulas 1-11 to 18 may be included:
[ chemical formulas 1 to 11]
[ chemical formulas 1 to 12]
[ chemical formulas 1 to 13]
[ chemical formulas 1 to 14]
[ chemical formulas 1 to 15]
[ chemical formulas 1 to 16]
[ chemical formulas 1 to 17]
[ chemical formulas 1 to 18]
In addition, the polymer of one embodiment of the present invention has a structure derived from an aromatic compound having 6 to 35 carbon atoms, so that the etching resistance and the heat resistance of the hard mask can be improved due to the high carbon content of the polymer without inhibiting the solubility and the flatness of the polymer.
In the present specification, the term "carbon content" may mean a ratio of the number of carbons to the total number of molecules of the compound.
The aromatic compound having 6 to 35 carbon atoms may include at least one of the following chemical formulas 2-1 to 2-6:
[ chemical formula 2-1]
[ chemical formula 2-2]
[ chemical formulas 2-3]
[ chemical formulas 2-4]
[ chemical formulas 2 to 5]
[ chemical formulas 2 to 6]
(wherein R is as defined above3One or more of the above aromatic compounds may be contained, and each is independently hydrogen or a hydroxyl group).
The aromatic compound having 6 to 35 carbon atoms may preferably be a pyrene compound, and the pyrene compound may be a compound of the chemical formula 2-1.
The polymer can be produced by a condensation reaction between the aromatic compound having 6 to 35 carbon atoms and the compound of chemical formula 1. In some examples, the polymer may be produced using only an aromatic compound having 6 to 35 carbon atoms and the compound of chemical formula 1, and other aromatic compounds or linking compounds may not be used in the production of the polymer. This prevents deterioration in flatness, etching resistance, and solubility due to addition of other compounds, and ensures desired physical properties.
For example, the aromatic compound having 6 to 35 carbon atoms and the compound of chemical formula 1 may be used in a molar ratio of 1:0.5 to 1:1, but not necessarily limited thereto.
For example, the above polymer may include a repeating unit of the following chemical formula 3:
[ chemical formula 3]
(in chemical formula 3, Ar)1Derived from the aromatic compound having 6 to 35 carbon atoms, wherein the aromatic compound having 6 to 35 carbon atoms may be further substituted with a hydroxyl group, Ar2Derived from the compound of the above chemical formula 1, n is an integer of 1 to 200),
specifically, the above polymer may be represented by the following chemical formula 3-1:
[ chemical formula 3-1]
(in the above chemical formula 3-1, Ar is described above1Ar is a functional group derived from the aromatic compound having 6 to 35 carbon atoms, Ar is independently a functional group derived from the aromatic compound having 6 to 20 carbon atoms, and R is4And R5Each independently represents a methyl group or an ethyl group, n1 is an integer of 1 to 200, and n2 is 0 or 1).
In an embodiment of the present invention, Ar is derived from an aromatic compound having 6 to 35 carbon atoms1For example, at least one selected from the group consisting of the following chemical formulas 3-11 to 3-16:
[ chemical formulas 3-11]
[ chemical formulas 3-12]
[ chemical formulas 3-13]
[ chemical formulas 3 to 14]
[ chemical formulas 3 to 15]
[ chemical formulas 3 to 16]
The two branches (branches) respectively drawn from the above chemical formulas 3-11 to 3-16 may be substituted instead of any two hydrogen atoms of each chemical formula, and the positions thereof are not limited to specific positions of each chemical formula, and only one of the two branches may be included if necessary.
In the above aromatic compound, R3May be one or more, and each independently may be hydrogen or a hydroxyl group.
In the embodiment of the present invention, the content of the polymer of the aromatic compound having 6 to 35 carbon atoms and the compound of chemical formula 1 is not particularly limited, and for example, may be 10 to 50% by weight based on the total weight of the hard mask composition, and when the above range is satisfied, the effect of the present invention can be exhibited most excellently.
In one embodiment, the weight average molecular weight of the polymer of the aromatic compound may be, for example, 1,500 to 10,000, and in the above range, suitable heat resistance, etching resistance and flatness can be simultaneously ensured.
In one embodiment, the Polydispersity index (PDI) of the aromatic polymer may be 1.5 to 6.0, and preferably 1.5 to 3.0. Within the above range, suitable heat resistance, etching resistance and flatness can be simultaneously ensured.
Solvent(s)
The solvent used in the composition for a hard mask according to the embodiment of the present invention is not particularly limited, and may contain an organic solvent having sufficient solubility for the polymer of the aromatic compound. For example, the solvent may include Propylene Glycol Monomethyl Ether Acetate (PGMEA), Propylene Glycol Monomethyl Ether (PGME), cyclohexanone, ethyl lactate, gamma-butyrolactone (GBL), acetylacetone (acetyl acetate), and the like.
The content of the solvent is not particularly limited, and may be the balance other than the polymer of the aromatic compound and the additional agent described later. For example, the content of the solvent may be 50 to 90% by weight based on the total weight of the composition for a hard mask, and the effect of the present invention can be effectively exhibited when the content satisfies the above range.
Supplementary preparation
Optionally, the hardmask composition according to an embodiment of the present invention may further include additional agents such as a crosslinking agent, a catalyst, and a surfactant.
The crosslinking agent is capable of crosslinking repeating units of the polymer of the aromatic compound, and is capable of reacting with, for example, hydroxyl groups of the polymer. The curing properties of the composition for a hard mask can be further enhanced by the crosslinking agent.
Examples of the crosslinking agent include melamine, amino resin, glycoluril compound, and diepoxy compound.
Specific examples of the crosslinking agent include etherified amino resins, such as methylated or butylated melamine (specifically, N-methoxymethyl-melamine or N-butoxymethyl-melamine) and methylated or butylated urea (urea) resin (specifically, Cymel U-65 resin or UFR 80 resin), glycoluril derivatives (see chemical formula 6, specifically, Powderlink 1174), bis (hydroxymethyl) -p-cresol compounds represented by chemical formula 7, and the like. Further, a diepoxy compound represented by the following chemical formula 8 and a melamine compound represented by the following chemical formula 9 may be used as the crosslinking agent.
[ chemical formula 6]
[ chemical formula 7]
[ chemical formula 8]
[ chemical formula 9]
As the catalyst, an acid catalyst or a basic catalyst can be used.
The acid catalyst may be a thermally activated acid catalyst. As an example of the acid catalyst, an organic acid such as p-toluenesulfonic acid can be used. As the above-mentioned acid catalyst, tooA compound of the Thermal Acid Generator (TAG) series can be used. Examples of the thermal acid generator catalyst include pyridinium p-toluenesulfonate
Salts (pyridine p-toluene sulfonate), 2,4,4, 6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, alkyl esters of organic sulfonic acids, and the like.
As the above-mentioned basic catalyst, a catalyst selected from NH may be used4OH or NR4Any one of ammonium hydroxides represented by OH (R is an alkyl group).
When the crosslinking agent is contained, the content of the crosslinking agent may be 1 to 30 parts by weight, preferably 5 to 20 parts by weight, and more preferably 5 to 10 parts by weight, based on 100 parts by weight of the polymer of the aromatic compound. When the catalyst is contained, the content of the catalyst may be 0.001 to 5 parts by weight, preferably 0.1 to 2 parts by weight, and more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the polymer of the aromatic compound.
Within the content ranges of the crosslinking agent and the catalyst, the polymer of the aromatic compound can have suitable crosslinking characteristics without deteriorating etching resistance, heat resistance, and flatness.
The composition for a hard mask according to an embodiment of the present invention may further include a surfactant in order to improve the surface properties and adhesion of the hard mask. As the surfactant, alkyl benzene sulfonate, alkyl pyridine may be used
Salts, polyethylene glycols, quaternary ammonium salts, and the like, but are not limited thereto. The surfactant may be contained in an amount of, for example, 0.1 to 10 parts by weight based on 100 parts by weight of the aromatic compound polymer.
Hereinafter, experimental examples including specific examples and comparative examples are provided to help understanding of the present invention, but they are merely to illustrate the present invention and do not limit the scope of the appended claims, and it is obvious to those skilled in the art that various changes and modifications may be made to the examples within the scope and technical spirit of the present invention, and such changes and modifications naturally fall within the scope of the appended claims.
Examples and comparative examples
Compositions for hard masks having the compositions and contents (wt%) shown in table 1 below were prepared. In examples and comparative examples, p-toluenesulfonic acid (5 mol% based on the aromatic compound) was used as an acid catalyst in the formation of the polymer (a).
[ Table 1]
A-1: by
(1:1 molar ratio) copolymer (weight-average molecular weight: 4500)
A-2: by
(1:1 molar ratio) of a copolymer (weight-average molecular weight: 5400)
A-3: by
(1:1 molar ratio) copolymer (weight-average molecular weight: 5500)
A-4: by
(1:1 molar ratio) of a copolymer (weight-average molecular weight: 5800)
A-5: by
(1:1 molar ratio) of a condensation reactionPolymer (weight average molecular weight: 4900)
A-6: by
(1:1 molar ratio) copolymer (weight-average molecular weight: 4300)
A-7: by
(1:1 molar ratio) copolymer (weight-average molecular weight: 5500)
A-8: by
(1:1 molar ratio) copolymer (weight-average molecular weight: 4700)
A-9: by
(1:1 molar ratio) copolymer (weight-average molecular weight: 4800)
A-10: by
(1:1 molar ratio) of a copolymer (weight-average molecular weight: 5300)
A-11: by
(1:1 molar ratio) copolymer (weight-average molecular weight: 5600)
A-12: by
(1:1 molar ratio) of a copolymer (weight-average molecular weight: 6000)
A-13: by
(1:1 molar ratio) copolymer (weight-average molecular weight: 510)0)
A' -1: by
(1:1 molar ratio) copolymer (weight-average molecular weight: 4000)
A' -2: by
(1:1 molar ratio) copolymer (weight-average molecular weight: 4300)
A' -3: by
(1:1 molar ratio) copolymer (weight-average molecular weight: 3600)
A' -4: by
(1:1 molar ratio) copolymer (weight-average molecular weight: 4000)
A' -5: by
(1:1 molar ratio) copolymer (weight-average molecular weight: 4300)
A' -6: by
(1:1 molar ratio) copolymer (weight-average molecular weight: 4800)
A' -7: by
(1:1 molar ratio) copolymer (weight-average molecular weight: 3500)
B-1：PGMEA
C-1: n-methoxymethyl-melamine resin
D-1: para-toluenesulfonic acid-pyridine
Salt (salt)
E-1: triethylene glycol
Examples of the experiments
The hard mask layers or hard masks formed from the compositions of table 1 were evaluated for etch resistance, solubility, and planarity by the evaluation methods described below. The evaluation results are shown in table 2 below.
(1) Evaluation of etching resistance
The compositions of examples and comparative examples were coated on silicon wafers by spin coating, respectively, and baked at 200 ℃ for 60 seconds to a thickness
The film of (1). The formed films were each coated with a photoresist for ArF, baked at 110 ℃ for 60 seconds, and then respectively exposed using an exposure apparatus of ASML (XT:1450G, NA 0.93) corporation, and then respectively developed using TMAH (2.38 wt% aqueous solution) to obtain a line and space (line and space) pattern of 60 nm.
The obtained patterned test piece was further cured at 110 ℃ for 60 seconds using CHF3/CF4The test piece was dry-etched with the mixed gas for 20 seconds, and the etching rate was measured by observing the cross section with an FE-SEM, thereby determining the etching resistance to halogen plasma.
< determination of etching resistance >
Very good: the etching speed is lower than 10A/Sec
O: an etching rate of 10A/Sec or more and less than 11A/Sec
And (delta): an etching rate of 11A/Sec or more and less than 12A/Sec
X: the etching rate is more than 12A/Sec
(2) Solubility in water
The compositions of examples and comparative examples in table 1 were dried, spin-coated to a thickness of 5um, dried in a hot air dryer at 100 ℃ for 3 minutes, and then the surfaces were visually observed. The solubility of the polymer was evaluated by the uniformity of the coating film.
< determination of solubility >
O: the unevenness of the coated surface was not confirmed with the naked eye
And (delta): local unevenness was visually confirmed
X: visually confirm that the entire surface was not uniform
(3) Evaluation of flatness
The compositions of examples and comparative examples were coated on SiO containing trenches having a width of 10 μm and a depth of 0.50. mu.m2A hard mask film was formed on a sheet substrate and dried, and a difference in thickness between a groove portion and a non-groove portion was observed by a Scanning Electron Microscope (SEM) to evaluate flatness.
< flatness determination >
O: the thickness difference is less than 150nm
And (delta): the thickness difference is 150-200 nm
X: the thickness difference exceeds 200nm
[ Table 2]
| Distinguishing | Etching resistance | Solubility in water | Flatness of |
| Example 1 | ◎ | ○ | ○ |
| Example 2 | ◎ | ○ | ○ |
| Example 3 | ◎ | ○ | ○ |
| Example 4 | ◎ | ○ | ○ |
| Example 5 | ○ | ○ | ○ |
| Example 6 | ◎ | ○ | ○ |
| Example 7 | ◎ | ○ | ○ |
| Example 8 | ○ | ○ | ○ |
| Example 9 | ○ | ○ | ○ |
| Example 10 | ○ | ○ | ○ |
| Example 11 | ◎ | ○ | ○ |
| Example 12 | ○ | ○ | ○ |
| Example 13 | ○ | ○ | ○ |
| Example 14 | ◎ | ○ | ○ |
| Example 15 | ◎ | ○ | ○ |
| Example 16 | ◎ | ○ | ○ |
| Example 17 | ◎ | △ | ○ |
| Comparative example 1 | ○ | △ | △ |
| Comparative example 2 | ○ | △ | △ |
| Comparative example 3 | △ | ○ | ○ |
| Comparative example 4 | △ | ○ | ○ |
| Comparative example 5 | ○ | × | × |
| Comparative example 6 | ◎ | × | × |
| Comparative example 7 | × | ○ | ○ |
Referring to table 2, in the case of examples using the aromatic compound disclosed in the present application and the compound of chemical formula 1, the etching resistance, solubility and flatness were excellent as a whole as compared to comparative examples.
In example 14, the result of the evaluation of the etching resistance was ∈ and it is described as the same as in example 1, but since the crosslinking agent and the catalyst were used together, the degree of crosslinking was improved and the etching resistance was further increased as compared with the case of example 1.
In example 16, since the content of the polymer (a) was small, there was a disadvantage that it was difficult to obtain a desired thickness when forming a hard mask layer or a hard mask.
In example 17, since the content of the polymer (a) was large, the effect of solubility and flatness was slightly lowered and the coating property was slightly inferior to those of the other examples.
Claims (7)
1. A composition for a hard mask, comprising a polymer formed by a condensation reaction of an aromatic compound comprising at least one compound selected from the group consisting of the following chemical formulas 2-1 to 2-6 and a compound of the following chemical formula 1; and a solvent:
chemical formula 1
In chemical formula 1, the R1And R2Each independently an alkyl group having 1 to 8 carbon atoms, which may be bonded to each other to form a ring,
the alkyl group may further comprise more than one oxygen atom in the backbone,
ar is a functional group derived from an aromatic compound having 6 to 20 carbon atoms,
chemical formula 2-1
Chemical formula 2-2
Chemical formula 2-3
Chemical formula 2-4
Chemical formula 2-5
Chemical formula 2-6
In the chemical formula 2-1-2-6, R3Independently represents one or more of the aromatic compounds represented by the chemical formulas 2-1 to 2-6, and independently represents hydrogen or hydroxyl.
2. The composition for a hard mask according to claim 1, wherein the Ar of the chemical formula 1 comprises at least one selected from the group consisting of the following chemical formulae Ar-1 to Ar-4:
chemical formula Ar-1
Chemical formula Ar-2
Chemical formula Ar-3
Chemical formula Ar-4
3. The composition for a hard mask according to claim 1, wherein the compound of chemical formula 1 comprises at least one selected from the group consisting of the following chemical formulae 1-1 to 1-5:
chemical formula 1-1
Chemical formula 1-2
Chemical formulas 1 to 3
Chemical formulas 1 to 4
Chemical formulas 1 to 5
Wherein Ar is a functional group derived from an aromatic compound having 6 to 20 carbon atoms.
4. The composition for a hard mask according to claim 1, the polymer comprising a repeating unit of the following chemical formula 3:
chemical formula 3
In chemical formula 3, Ar1Derived from an aromatic compound consisting of at least one compound selected from the group consisting of the chemical formulas 2-1 to 2-6, and may be further substituted with a hydroxyl group,
ar is2A compound derived from the compound of the chemical formula 1,
n is an integer of 1 to 200.
5. The composition for a hard mask according to claim 1, the polymer is represented by the following chemical formula 3-1:
chemical formula 3-1
In the chemical formula 3-1, Ar1Derived from an aromatic compound composed of at least one compound selected from the group consisting of the chemical formulas 2-1 to 2-6,
ar is a functional group derived from an aromatic compound having 6 to 20 carbon atoms,
the R is4And R5Each independently being a methyl group or an ethyl group,
n1 is an integer of 1 to 200,
the n2 is 0 or 1.
6. The composition for a hard mask as claimed in claim 4, the polymer consists of Ar only1And Ar2And (4) forming.
7. The composition for a hard mask according to claim 1, further comprising at least one of a crosslinking agent, a catalyst and a surfactant.
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| KR10-2017-0020664 | 2017-02-15 | ||
| KR1020170020664A KR101775586B1 (en) | 2017-02-15 | 2017-02-15 | Composition for hard mask |
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| KR102260811B1 (en) | 2018-12-26 | 2021-06-03 | 삼성에스디아이 주식회사 | Hardmask composition, hardmask layer and method of forming patterns |
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| EP2469338B1 (en) * | 2009-08-19 | 2014-11-19 | Nissan Chemical Industries, Ltd. | Resist underlayer film-forming composition for lithography containing resin having aliphatic ring and aromatic ring |
| WO2013080929A1 (en) * | 2011-12-01 | 2013-06-06 | Jsr株式会社 | Resist-underlayer-film-forming composition used in multilayer resist process, resist underlayer film, method for forming same, and pattern-formation method |
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