KR101862711B1 - Compound, organic layer composition, organic layer, and method of forming patterns - Google Patents
Compound, organic layer composition, organic layer, and method of forming patterns Download PDFInfo
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- KR101862711B1 KR101862711B1 KR1020150076593A KR20150076593A KR101862711B1 KR 101862711 B1 KR101862711 B1 KR 101862711B1 KR 1020150076593 A KR1020150076593 A KR 1020150076593A KR 20150076593 A KR20150076593 A KR 20150076593A KR 101862711 B1 KR101862711 B1 KR 101862711B1
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- C07C50/22—Quinones the quinoid structure being part of a condensed ring system containing four or more rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/10—Quinones the quinoid structure being part of a condensed ring system containing two rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/26—Quinones containing groups having oxygen atoms singly bound to carbon atoms
- C07C50/32—Quinones containing groups having oxygen atoms singly bound to carbon atoms the quinoid structure being part of a condensed ring system having two rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C50/00—Quinones
- C07C50/26—Quinones containing groups having oxygen atoms singly bound to carbon atoms
- C07C50/36—Quinones containing groups having oxygen atoms singly bound to carbon atoms the quinoid structure being part of a condensed ring system having four or more rings
Abstract
A compound in which a first compound represented by the general formula (1) and a second compound which is a substituted or unsubstituted C6 to C80 aromatic ring group, a substituted or unsubstituted C2 to C80 heteroaromatic ring group, or a combination thereof is produced by a condensation reaction . The definition of the above formula (1) is as described in the specification.
Description
The present invention relates to a novel compound, an organic film composition containing the compound, an organic film prepared from the 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. Thus, the hardmask layer needs to have corrosion-resisting properties to withstand multiple etching processes.
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 a compound having good corrosion resistance and good solubility characteristics.
Another embodiment provides an organic film composition comprising such a compound.
Another embodiment provides an organic film that simultaneously satisfies both mechanical properties and film flatness.
Another embodiment provides a method of forming a pattern using the organic film composition.
According to one embodiment, a first compound represented by the following formula (1), and a second compound represented by the following formula (1), and a substituted or unsubstituted C6 to C80 aromatic ring group, a substituted or unsubstituted C2 to C80 heteroaromatic ring group, To give a compound produced by the condensation reaction.
[Chemical Formula 1]
In Formula 1,
X is a substituted or unsubstituted C12 to C80 fused cyclic group.
The first compound may be any one selected from the following Group 1.
[Group 1]
In the group 1,
Z a and Z b are each independently C═O, oxygen (O), sulfur (S), CR x R y , NR z , or combinations thereof wherein R x to R z are each independently hydrogen, Or an unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,
Z c and Z d are each independently nitrogen (N), CR w Or a combination thereof, wherein Rw is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof.
The second compound may be any one selected from the following Group 2, or any one selected from the following Group 2, substituted by at least one hydroxy group.
[Group 2]
In the group 2,
Z 1 and Z 2 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, Substituted or unsubstituted C2 to C20 alkenylene groups, substituted or unsubstituted C2 to C20 alkynylene groups, C═O, NR a , oxygen (O), sulfur (S), or a substituted or unsubstituted C2 to C20 heteroarylene group, , Wherein R a is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,
Z 3 to Z 20 and Z 23 to Z 25 each independently represent C═O, oxygen (O), sulfur (S), CR b R c , NR d , or combinations thereof wherein R b to R d are Each independently represents hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,
Z 21 and Z 22 are each independently nitrogen (N), CR e Or a combination thereof, wherein R e is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof. ≪ / RTI >
(2)
In Formula 2,
Y is a substituted or unsubstituted C12 to C80 fused cyclic group,
* Is the connection point.
The moiety represented by Formula 2 may be any one selected from Group 3 below.
[Group 3]
In the group 3,
Z a and Z b are each independently C═O, oxygen (O), sulfur (S), CR x R y , NR z , or combinations thereof wherein R x to R z are each independently hydrogen, Or an unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,
Z c and Z d are each independently nitrogen (N), CR w Or a combination thereof, wherein Rw is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
* Is the connection point.
The compound may include a structural unit represented by any one of the following formulas (2a) to (2f).
(2a)
(2b)
[Chemical Formula 2c]
(2d)
[Formula 2e]
(2f)
In the above general formulas (2a) to (2f)
Ar is a substituted or unsubstituted C6 to C80 aromatic ring group, a substituted or unsubstituted C2 to C80 hetero aromatic ring group, or a combination thereof,
n is an integer of 1 to 200,
* Is the connection point.
However, when n = 1, * is hydrogen.
In the above formulas (2a) to (2f), Ar may be any one selected from the group 2.
The compound may be a polymer having a weight average molecular weight of 500 to 20,000.
The compound may be a monomer having a molecular weight of 500 to 1,000.
According to another embodiment, there is provided an organic film composition comprising the above-described compound, and a solvent.
The compound 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.
According to another embodiment, there is provided an organic film in which the above-mentioned organic film composition is cured to be formed.
The organic layer may include a hard mask layer.
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.
And forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist layer.
The present invention provides a novel compound that has excellent corrosion resistance and good solubility characteristics and can be applied to a spin-on coating system.
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.
The compounds according to one embodiment are described below.
A compound according to one embodiment is a first compound represented by Formula 1 and a second compound that is a substituted or unsubstituted C6 to C80 ring group, a substituted or unsubstituted C6 to C80 heterocyclic group, or a combination thereof: Condensation reaction.
[Chemical Formula 1]
In Formula 1,
X is a substituted or unsubstituted C12 to C80 fused cyclic group. The compound according to one embodiment is produced by condensation reaction of these compounds, starting from a first compound which is a dicarbonyl compound and a second compound which is an aromatic ring group.
First, the first compound will be described.
The first compound has a structure in which two carbonyl groups are contained in a substituted or unsubstituted C 12 to C 80 fused cyclic group.
The fused ring group may be a ring group formed by fusing two or more benzene rings, (ii) a ring group formed by fusing two or more C5 to C8 aliphatic ring groups, or (iii) one or two or more benzene rings, and Or a cyclic group formed by fusing two or more C5 to C8 aliphatic cyclic groups. For example, the fused ring group may include at least two substituted or unsubstituted benzene rings in its structure. The fused ring group may be, for example, naphthalene, anthracene, phenanthrene, pyrene, perylene, benzoperylene, and coronene, but is not limited thereto.
As another example, the fused ring group may be a group including a group represented by the following formula (4), but is not limited thereto.
[Group 4]
The first compound of the dicarbonyl structure including the fused ring group may be, for example, any of the compounds listed in the following Group 1, but is not limited thereto.
[Group 1]
In the group 1,
Z a and Z b are each independently C═O, oxygen (O), sulfur (S), CR x R y , NR z , or combinations thereof wherein R x to R z are each independently hydrogen, Or an unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,
Z c and Z d are each independently nitrogen (N), CR w Or a combination thereof, wherein Rw is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof.
In the group 1, Z a and Z b may be, for example, NH, and Z c and Z d may be, for example, CH or N, but are not limited thereto.
As described above, the first compound is condensed with a second compound containing an aromatic ring group to produce a novel compound of interest.
The second compound is described below.
The second compound is not limited as long as the number of carbon atoms of the substituted or unsubstituted C6 to C80 aromatic ring group, substituted or unsubstituted C2 to C80 heteroaromatic ring group, or combination thereof is within the above range. The heteroaromatic ring group contained in the heteroaromatic ring group may be, for example, N, O, S and P, and the heteroaromatic ring group may contain, for example, 1 to 3 at least one selected from N, O, S and P.
For example, the second compound may be a substituted or unsubstituted compound selected from the following Group 2, but is not limited thereto.
[Group 2]
In the group 2,
Z 1 and Z 2 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, Substituted or unsubstituted C2 to C20 alkenylene groups, substituted or unsubstituted C2 to C20 alkynylene groups, C═O, NR a , oxygen (O), sulfur (S), or a substituted or unsubstituted C2 to C20 heteroarylene group, , Wherein R a is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,
Z 3 to Z 20 and Z 23 to Z 25 each independently represent C═O, oxygen (O), sulfur (S), CR b R c , NR d , or combinations thereof wherein R b to R d are Each independently represents hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,
Z 21 and Z 22 are each independently nitrogen (N), CR e Or a combination thereof, wherein R e is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof.
For example, the second compound may be, for example, a substituted or unsubstituted polycyclic aromatic ring group, and may be, for example, substituted or unsubstituted naphthalene, substituted or unsubstituted anthracene, substituted or unsubstituted pyrene, Substituted or unsubstituted phenanthrene, substituted or unsubstituted benzene perylene, substituted or unsubstituted perylene, substituted or unsubstituted benzene perylene, substituted or unsubstituted coronene, substituted or unsubstituted triphenylene, substituted or unsubstituted phenanthrene, substituted or unsubstituted corannulene, , And substituted or unsubstituted chrysene (Chrysene).
For example, the second compound may be substituted by, for example, a hydroxy group, wherein the substitution position and the number are not limited.
Since the compound is obtained by a condensation reaction of a first compound containing a fused ring group containing two carbonyl groups in a molecule and a second compound containing an aromatic ring group or a heteroaromatic ring group, Compound synthesis is possible. Therefore, while the ring parameter and the carbon content of the resulting compound increase at the same time, the annular carbonyl group is converted into the hydroxyl group during the synthesis of the compound, so that the corrosion resistance and solubility, which are the conflicting properties, can be secured at the same time.
According to another embodiment, there is provided a compound comprising a moiety represented by the following formula (2).
(2)
In Formula 2,
Y is a substituted or unsubstituted C12 to C80 fused cyclic group,
* Is the connection point.
For example, the moiety represented by Formula 2 may be any moiety listed in Group 3 below, but is not limited thereto.
[Group 3]
In the group 3,
Z a and Z b are each independently C═O, oxygen (O), sulfur (S), CR x R y , NR z , or combinations thereof wherein R x to R z are each independently hydrogen, Or an unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,
Z c and Z d are each independently nitrogen (N), CR w Or a combination thereof, wherein Rw is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
* Is the connection point.
The compound containing a moiety represented by the formula (2) is a dihydroxy compound having a fused ring group as a core and having two hydroxyl groups substituted on both sides thereof.
In Formula 2, Y may include, for example, two benzene rings.
The dihydroxy compound may be produced, for example, by a condensation reaction of a dicarbonyl compound and an " aromatic ring group compound ". Here, the dicarbonyl compound may be the first compound represented by the above-mentioned formula (1), and the aromatic ring group may be a substituted or unsubstituted C6 to C80 aromatic ring group, a substituted or unsubstituted C2 to C80 hetero An aromatic ring group, or a combination thereof, but is not limited thereto.
The dihydroxy compound is excellent in corrosion resistance and solubility, and the binding force to a silicon wafer (for example, an SiO 2 wafer) can be improved as the hydroxy group is present in the final structure.
The above-mentioned novel compounds obtained by the condensation reaction of the first compound and the second compound and the above-mentioned novel compounds containing the moiety represented by the general formula (2) are specifically represented by structural units But is not limited thereto.
(2a)
(2b)
[Chemical Formula 2c]
(2d)
[Formula 2e]
(2f)
In the above general formulas (2a) to (2f)
Ar is a substituted or unsubstituted C6 to C80 aromatic ring group, a substituted or unsubstituted C2 to C80 hetero aromatic ring group, or a combination thereof,
n is an integer of 1 to 200,
* Is the connection point.
For example, in the above formulas (2a) to (2f), Ar may be any one selected from the following Group 2, or any one selected from the following Group 2, substituted by at least one hydroxy group, but is not limited thereto.
[Group 2]
In the group 2,
Z 1 and Z 2 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, Substituted or unsubstituted C2 to C20 alkenylene groups, substituted or unsubstituted C2 to C20 alkynylene groups, C═O, NR a , oxygen (O), sulfur (S), or a substituted or unsubstituted C2 to C20 heteroarylene group, , Wherein R a is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,
Z 3 to Z 20 and Z 23 to Z 25 each independently represent C═O, oxygen (O), sulfur (S), CR b R c , NR d , or combinations thereof wherein R b to R d are Each independently represents hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,
Z 21 and Z 22 are each independently nitrogen (N), CR e Or a combination thereof, wherein R e is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof.
The novel compound obtained by the condensation reaction of the first compound and the second compound described above and the novel compound containing the moiety represented by the general formula 2 described above is, for example, a monomer having a molecular weight of about 500 to 1,000, But is not limited to, a polymer having a weight average molecular weight of about 500 to 20,000.
According to another embodiment, a novel compound obtained by the condensation reaction of the first compound and the second compound described above, or a novel compound containing a moiety represented by the general formula (2) described above, and an organic film containing a solvent Lt; / RTI >
When the above compound is used as an organic film material, it is possible to form a uniform thin film without forming pin-holes and voids or deteriorate thickness scattering in the baking process, or when a step is present in the lower substrate (or film) It is possible to provide excellent gap-fill and planarization characteristics.
In addition, since the hydroxyl group attached to the high carbon chain of the compound is excellent in adhesion to a silicon wafer, the compound can form a film having excellent corrosion resistance as well as excellent coating properties.
The solvent is not particularly limited as long as it has sufficient solubility or dispersibility in the compound. Examples of the solvent include propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) But are not limited to, methyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N, N-dimethylformamide, , Methyl pyrrolidinone, acetylacetone, and ethyl 3-ethoxypropionate.
The compound may be included in an amount of about 0.1 to 50% by weight based on the total amount of the organic film composition. By including the compound 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, as the crosslinking agent having at least two crosslinking substituents, for example, methoxymethylated glycoluril, butoxymethylated glyceryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxy Methylated benzoguanamine, a methoxymethylated urea, a butoxymethylated urea, a methoxymethylated thioether, or a methoxymethylated thioether.
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.
A patterning method according to an embodiment includes the steps of providing a material layer on a substrate, applying an organic film composition including the above-described compound and a solvent on the material layer, heat treating the organic film composition to form a hard mask layer 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 a mask to expose 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, the heat treatment process may be performed at about 100 to 500 ° 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
Synthetic example One
(0.1 mole) of the compound A (first compound), 14.4 g (0.1 mole) of 1-naphthol (second compound), 5 g of sulfuric acid, 5.3 g of 3-mercaptopropionic acid and 160 g of Toluene were placed in a flask, Lt; / RTI > 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 2500 to 3500. When the reaction was completed, ethyl acetate and purified water were added to extract the organic layer. The organic layer was concentrated under reduced pressure, and then methanol was added to form a precipitate. This was filtered to obtain a compound represented by the following formula (A) (weight average molecular weight (Mw) = 3,300).
(A)
Synthetic example 2
The flask was charged with 28.2 g (0.1 mole) of compound A (the first compound), 21.8 g (0.1 mole) of hydroxypyrrene (second compound), 5 g of sulfuric acid, 5.3 g of 3-mercaptopropionic acid and 160 g of toluene, Lt; / RTI > 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 2500 to 3500. When the reaction was completed, ethyl acetate and purified water were added to extract the organic layer. The organic layer was concentrated under reduced pressure, and then methanol was added to form a precipitate. This was filtered to obtain a compound represented by the following formula (B) (weight average molecular weight (Mw) = 3,300).
[Chemical Formula B]
Synthetic example 3
(0.1 mol) of compound B (the first compound), 14.4 g (0.1 mol) of 1-naphthol (the second compound), 5 g of sulfuric acid, 5.3 g of 3-mercaptopropionic acid and 160 g of Toluene, Lt; / RTI > 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 2500 to 3500. When the reaction was completed, ethyl acetate and purified water were added to extract the organic layer. The organic layer was concentrated under reduced pressure, and then methanol was added to form a precipitate. This was filtered to obtain a compound represented by the following formula (C) (weight average molecular weight (Mw) = 3,300).
≪ RTI ID = 0.0 &
Synthetic example 4
To the flask was added 33.2 g (0.1 mole) of compound B (first compound), 21.8 g (0.1 mole) of hydroxypyrrene (second compound), 5 g of sulfuric acid, 5.3 g of 3-mercaptopropionic acid and 160 g of toluene. 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 2500 to 3500. When the reaction was completed, ethyl acetate and purified water were added to extract the organic layer. The organic layer was concentrated under reduced pressure, and then methanol was added to form a precipitate. This was filtered to obtain a compound represented by the following formula (D) (weight average molecular weight (Mw) = 3,300).
[Chemical Formula D]
Synthetic example 5
The flask was charged with 45.6 g (0.1 mole) of the compound C (the first compound), 14.4 g (0.1 mole) of 1-naphthol (the second compound), 7 g of sulfuric acid, 7.4 g of 3-mercaptopropionic acid and 180 g of Dioxane, Respectively. 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 2500 to 3500. When the reaction was completed, ethyl acetate and purified water were added to extract the organic layer. The organic layer was concentrated under reduced pressure, and then methanol was added to form a precipitate. This was filtered to obtain a compound represented by the following formula (E) (weight average molecular weight (Mw) = 3,300).
(E)
Synthetic example 6
45.6 g (0.1 mole) of compound C (first compound), 21.8 g (0.1 mole) of hydroxypyrrene (second compound), 7 g of sulfuric acid, 7.4 g of 3-mercaptopropionic acid and 180 g of Dioxane were added to the flask and stirred at 100 ° C . 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 2500 to 3500. When the reaction was completed, ethyl acetate and purified water were added to extract the organic layer. The organic layer was concentrated under reduced pressure, and then methanol was added to form a precipitate. This was filtered to obtain a compound represented by the following formula (F) (weight average molecular weight (Mw) = 3,300).
[Chemical Formula F]
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. ) Were sequentially added and dissolved in 51 g of propylene glycol monomethyl ether acetate (PGMEA). Then, 0.15 g (0.001 mol) of diethylsulfite was added thereto, followed by stirring at 90 to 120 ° for 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). 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 the methanol and distilled water remaining in the solution were removed under reduced pressure to obtain a polymer (Mw: 2500) represented by the following formula (G).
[Formula G]
Comparative 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, a polymer (Mw: 2500) represented by the following formula (H) was obtained in the same manner as in Comparative Synthesis Example 1.
[Formula H] <
Hard mask Preparation of composition
Example One
1.5 g of the compound obtained in Synthesis Example 1 was dissolved in 10 g of a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7: 3 (v / v) To prepare a hard mask composition.
Example 2 to 6
A hard mask composition was prepared in the same manner as in Example 1, except that the compounds obtained in Synthesis Examples 2 to 6 were used in place of the compounds obtained in Synthesis Example 1.
Comparative Example 1 and 2
A hard mask composition was prepared in the same manner as in Example 1, except that the compounds obtained in Comparative Synthesis Examples 1 and 2 were used instead of the compounds obtained in Synthesis Example 1.
Rating 1: Awareness of corrosion evaluation
The hard mask composition containing the compounds according to Examples 1 to 6 and Comparative Examples 1 and 2 was applied on a silicon wafer by a spin-on coating method, and then heat-treated at 400 DEG C for 90 seconds on a hot plate to form a thin film having a thickness of 4,000 ANGSTROM .
The formed thin film was dry etched for 100 seconds and 60 seconds using CFx and N 2 / O 2 mixed gas, respectively, and the thickness of the remaining film was measured. The corrosion resilience of thin films was compared with the bulk etch rate (BER) as in Equation (1).
The results are shown in Table 1.
[Equation 1]
Bulk etch rate (BER) = (initial thin film thickness - thin film thickness after etching) / etching time (seconds)
Referring to Table 1, it can be seen that the thin film formed from the hard mask composition according to Examples 1 to 6 has a lower etching rate than the thin film formed from the hard mask composition according to Comparative Examples 1 and 2.
From these results, it can be seen that the hard mask composition according to Examples 1 to 6 has higher corrosion resistance of the thin film as compared with Comparative Examples 1 and 2.
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 (21)
menstruum
: ≪ / RTI >
[Chemical Formula 1]
In Formula 1,
X is a substituted or unsubstituted C12 to C80 fused cyclic group.
(2a)
(2b)
[Chemical Formula 2c]
(2d)
[Formula 2e]
(2f)
In the above general formulas (2a) to (2f)
Ar is a substituted or unsubstituted C6 to C80 aromatic ring group, a substituted or unsubstituted C2 to C80 hetero aromatic ring group, or a combination thereof,
n is an integer of 1 to 200,
* Is the connection point.
However, when n = 1, * is hydrogen.
The term "substituted or unsubstituted" as used herein means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxyl group, a nitro group, a cyano group, an amino group, an azido 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 C2 to C20 alkenyl group, a C2 to C20 alkenyl group, A C3 to C30 heteroaryl group, a C3 to C30 cycloalkyl group, a C3 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C2 to C20 hetero aryl group, Substituted by a substituent selected from a cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof.
Wherein the first compound is any one selected from the following Group 1:
[Group 1]
In the group 1,
Z a and Z b are each NH,
Z c and Z d are each N.
Wherein the second compound is any one selected from the following Group 2, or any one selected from the following Group 2 is substituted by at least one hydroxy group:
[Group 2]
In the group 2,
Z 1 and Z 2 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, Substituted or unsubstituted C2 to C20 alkenylene groups, substituted or unsubstituted C2 to C20 alkynylene groups, C═O, NR a , oxygen (O), sulfur (S), or a substituted or unsubstituted C2 to C20 heteroarylene group, , Wherein R a is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,
Z 3 to Z 20 and Z 23 to Z 25 each independently represent C═O, oxygen (O), sulfur (S), CR b R c , NR d , or combinations thereof wherein R b to R d are Each independently represents hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,
Z 21 and Z 22 are each independently nitrogen (N), CR e, or a combination thereof, wherein R e is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof.
The term "substituted or unsubstituted" as used herein means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxyl group, a nitro group, a cyano group, an amino group, an azido 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 C2 to C20 alkenyl group, a C2 to C20 alkenyl group, A C3 to C30 heteroaryl group, a C3 to C30 cycloalkyl group, a C3 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C2 to C20 hetero aryl group, Substituted by a substituent selected from a cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof.
Wherein Ar is any one selected from the following Group 2 or any one selected from the following Group 2 is substituted by at least one hydroxy group:
[Group 2]
In the group 2,
Z 1 and Z 2 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, Substituted or unsubstituted C2 to C20 alkenylene groups, substituted or unsubstituted C2 to C20 alkynylene groups, C═O, NR a , oxygen (O), sulfur (S), or a substituted or unsubstituted C2 to C20 heteroarylene group, , Wherein R a is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,
Z 3 to Z 20 and Z 23 to Z 25 each independently represent C═O, oxygen (O), sulfur (S), CR b R c , NR d , or combinations thereof wherein R b to R d are Each independently represents hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof,
Z 21 and Z 22 are each independently nitrogen (N), CR e, or a combination thereof, wherein R e is hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, or a combination thereof.
The term "substituted or unsubstituted" as used herein means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxyl group, a nitro group, a cyano group, an amino group, an azido 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 C2 to C20 alkenyl group, a C2 to C20 alkenyl group, A C3 to C30 heteroaryl group, a C3 to C30 cycloalkyl group, a C3 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C2 to C20 hetero aryl group, Substituted by a substituent selected from a cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and combinations thereof.
Wherein the organic film comprises a hard mask layer.
Applying the organic film composition according to claim 10 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 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 >
Wherein the step of applying the organic film composition is performed by a spin-on coating method.
Further comprising forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist layer.
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