KR101806329B1 - Monomer, polymer, organic layer composition, organic layer, and method of forming patterns - Google Patents
Monomer, polymer, organic layer composition, organic layer, and method of forming patterns Download PDFInfo
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- KR101806329B1 KR101806329B1 KR1020150109027A KR20150109027A KR101806329B1 KR 101806329 B1 KR101806329 B1 KR 101806329B1 KR 1020150109027 A KR1020150109027 A KR 1020150109027A KR 20150109027 A KR20150109027 A KR 20150109027A KR 101806329 B1 KR101806329 B1 KR 101806329B1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
An organic film composition comprising a monomer represented by the formula (1), a polymer represented by the formula (2), the monomer, the polymer, or a combination thereof, a compound for an organic film, an organic film prepared from the organic film composition, And a method for forming a pattern using the same.
The definitions of the above formulas (1) and (2) are as described in the specification.
Description
To novel monomers and polymers. The present invention also relates to an organic film composition comprising the monomer, the polymer, or a combination thereof, an organic film made from the organic film composition, and a pattern forming method using the organic film composition.
BACKGROUND ART [0002] In recent years, the semiconductor industry has developed into an ultrafine technology having a pattern of a few to a few nanometers in a pattern of a size of several hundred nanometers. Effective lithographic techniques are essential to realize this ultrafine technology.
A typical lithographic technique involves forming a material layer on a semiconductor substrate, coating a photoresist layer thereon, exposing and developing the photoresist layer to form a photoresist pattern, and etching the material layer using the photoresist pattern as a mask do.
In recent years, as the size of a pattern to be formed decreases, it is difficult to form a fine pattern having a good profile only by the typical lithographic technique described above. Accordingly, a fine pattern can be formed by forming an organic film called a hardmask layer between the material layer to be etched and the photoresist layer.
The hard mask layer acts as an interlayer to transfer the fine pattern of the photoresist to the material layer through the selective etching process. Therefore, the hard mask layer needs to have heat resistance and resistance to erosion resistance so as to withstand the multiple etching process.
Meanwhile, it has recently been proposed that the hard mask layer is formed by a spin-on coating method instead of the chemical vapor deposition method. The spin-on coating method is not only easy to process but also can improve gap-fill and planarization properties. In order to realize a fine pattern, it is necessary to form multiple patterns. In this case, the embedding characteristic of embedding the pattern in the film without voids is required. Further, in the case where there is a step on the substrate to be processed, or in the case where a pattern dense portion and an area having no pattern exist together on the wafer, it is necessary to planarize the film surface by the underlayer film.
There is a demand for an organic film material that can satisfy the above-mentioned characteristics.
One embodiment provides a monomer capable of simultaneously ensuring corrosion-resisting and planarizing properties.
Another embodiment provides a polymer capable of simultaneously ensuring corrosion-resisting and planarizing properties.
Another embodiment provides an organic film composition comprising a compound for an organic film, which is the monomer, the polymer, or a combination thereof.
Another embodiment provides an organic film capable of securing corrosion resistance and planarization characteristics at the same time.
Another embodiment provides a pattern formation method using the organic film composition.
According to one embodiment, there is provided a monomer represented by the following general formula (1).
[Chemical Formula 1]
In Formula 1,
A 1 , A 2 , A 3 , A 4 and A 5 are each independently a substituted or unsubstituted aromatic ring group,
X 1 , X 2 , X 3 and X 4 each independently represent a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, an oxygen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group , A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group, A substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof,
Each of C 1 , C 2 , C 3 , C 4 , D 1 , D 2 , D 3 , D 4 , E 1 , E 2 , E 3 and E 4 independently represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted amino group , A halogen atom, an oxygen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkenyl group , A substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, A substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof ,
a, b and c are each independently 0 or 1;
In Formula 1, A 1 , A 2 , A 3 , A 4, and A 5 each independently represent a substituted or unsubstituted aromatic ring group selected from the groups listed in Group 1 below.
[Group 1]
In the group 1,
Z 1 represents 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, a substituted or unsubstituted C2 to C20 heteroaryl (O), sulfur (S), or a combination thereof, wherein R is a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, a is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, a halogen atom,
Z 3 to Z 18 each independently represent C = O, NR a , oxygen (O), sulfur (S), CR b R c Or a combination thereof, wherein each of R a to R c is independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group , A halogen atom, a halogen-containing group, or a combination thereof.
In Formula 1, at least one of X 1 and X 2 may be a hydroxy group.
In Formula 1, a, b and c are 1, and at least one of X 3 and X 4 is a hydroxy group.
In Formula 1, a is 0, b and c are 1, and at least one of X 3 and X 4 is a hydroxy group.
In the general formula (1) wherein the C 1, D 1 and E at least one of the first is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, wherein the C 2, D 2 And E < 2 > may be a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.
Wherein a, b and c are 1, at least one of C 3 , D 3 and E 3 is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, And at least one of C 4 , D 4 and E 4 may be a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.
Wherein c is 1 and at least one of A 1 , A 2 and A 3 is an aromatic ring group substituted with one or more methoxy group (-OCH 3 ) or ethoxy group (-OC 2 H 5 ) Lt; / RTI >
Wherein a, b and c are 1, and at least one of A 4 and A 5 is an aromatic ring substituted with one or more methoxy group (-OCH 3 ) or ethoxy group (-OC 2 H 5 ) .
The monomer may have a molecular weight of 800 to 5000.
According to another embodiment, there is provided a polymer represented by the following formula (2).
(2)
In Formula 2,
A 1 , A 2 , A 3 , A 4 and A 5 are each independently a substituted or unsubstituted aromatic ring group,
X 1 , X 2 , X 3 and X 4 each independently represent a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, an oxygen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group , A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group, A substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof,
Each of C 1 , C 2 , C 3 , C 4 , D 1 , D 2 , D 3 , D 4 , E 1 , E 2 , E 3 and E 4 independently represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted amino group , A halogen atom, an oxygen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkenyl group , A substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, A substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof ,
a, b and c are each independently 0 or 1,
n is an integer of 1 to 500;
In Formula 2, A 1 , A 2 , A 3 , A 4, and A 5 are each independently a substituted or unsubstituted aromatic ring group selected from the groups listed in Group 1.
In Formula 2, at least one of X 1 and X 2 may be a hydroxy group.
In Formula 2, a is 0, b and c are 1, and at least one of X 3 and X 4 is a hydroxy group.
In the formula 2, wherein C 1, D 1 and E at least one of the first is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, wherein the C 2, D 2 and E 2 may be a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.
In Formula 2, a is 0, b and c are 1, and at least one of C 3 , D 3 and E 3 is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, Or a combination thereof, and at least one of C 4 , D 4, and E 4 may be a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.
In Formula 2, a is 0 and b and c are 1, and wherein A 1, A 2, A 3 and A 4 at least one of which is a methoxy group or one or more 2 (-OCH 3) or ethoxy group (-OC 2 H < 5 >) group.
The weight average molecular weight of the polymer may be from 1,000 to 200,000.
According to another embodiment, there is provided an organic film composition comprising a solvent, a compound for an organic film which is the above-mentioned monomer, the polymer described above, or a combination thereof.
The organic film compound may be contained in an amount of 0.1% by weight to 30% 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 and formed.
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; curing the organic film composition to form a hard mask layer; Containing thin film layer, a step of forming a photoresist layer on the silicon-containing thin film layer, a step of exposing and developing the photoresist layer to form a photoresist pattern, a step of forming the silicon- Selectively removing the hard mask layer and exposing a portion of the material layer, and etching the exposed portion of the material layer.
The step of applying the organic film composition may be performed by a spin-on coating method.
The silicon-containing thin film layer may comprise SiCN, SiOC, SiON, SiOCN, SiC, SiN, or a combination thereof.
And forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist layer.
It is possible to provide an organic film which can secure both corrosion resistance and planarization characteristics.
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 the hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino 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 C2 to C20 alkenyl group, a C2 to C20 alkenyl group, A C5 to C30 arylalkyl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 hetero aryl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, 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.
Also, unless otherwise defined herein, '*' refers to the point of attachment of a compound or moiety.
The monomers according to one embodiment will be described below.
The monomers according to one embodiment are represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
A 1 , A 2 , A 3 , A 4 and A 5 are each independently a substituted or unsubstituted aromatic ring group,
X 1 , X 2 , X 3 and X 4 each independently represent a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, an oxygen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group , A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group, A substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof,
Each of C 1 , C 2 , C 3 , C 4 , D 1 , D 2 , D 3 , D 4 , E 1 , E 2 , E 3 and E 4 independently represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted amino group , A halogen atom, an oxygen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkenyl group , A substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, A substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof ,
a, b and c are each independently 0 or 1;
For example, a and b in the formula (1) may be 0 and c may be 1. For example, a, b and c in the above formula (1) may be 1.
The monomer has a structure in which a quaternary carbon is located between two substituted or unsubstituted aromatic ring groups. In the present specification, a quaternary carbon is defined as a carbon in which all four of four hydrogen atoms bonded to carbon are replaced with a group other than hydrogen.
Since the monomer has a structure containing quaternary carbon, the solubility is improved and is advantageously applied to the spin-on coating method.
[Reaction Scheme 1]
The reaction scheme 1 is an exemplary illustration of a reaction in which the functional groups represented by X 1 and E 1 are removed during the high-temperature curing of the monomer. According to such a reaction, the cured film formed using the monomer may have an excellent film density.
The functional groups represented by X 1 , X 2 , X 3 and X 4 and the functional groups represented by C 1 , C 2 , C 3 , C 4 , D 1 , D 2 , D 3 , D 4 , E 1 and E 2 , E 3 and E 4 may be eliminated or cyclized by high temperature curing of the monomers.
For example, in Formula 1, at least one of X 1 and X 2 may be a hydroxy group. For example, when a, b, and c are 1, at least one of X 3 and X 4 is a hydroxy group, 0 and b and c are 1, at least one of X 3 and X 4 may be a hydroxy group, but is not limited thereto.
For example, in Formula 1, C 1, D 1 and E at least one of the first is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, wherein the C 2 , And at least one of D 2 and E 2 may be a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, and wherein a, b, and c in the above formula If 1, the C 3, D 3 and E at least one of the three is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, wherein the C 4, D 4 and E 4 may be a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, but is not limited thereto.
On the other hand, the monomer may contain an aromatic ring group to secure a rigid property.
In formula (1), A 1 , A 2 , A 3 , A 4 and A 5 each representing a substituted or unsubstituted aromatic ring group may be independently selected from the groups listed in the following group 1.
[Group 1]
In the group 1,
Z 1 represents 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, a substituted or unsubstituted C2 to C20 heteroaryl (O), sulfur (S), or a combination thereof, wherein R is a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, a is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, a halogen atom,
Z 3 to Z 18 each independently represent C = O, NR a , oxygen (O), sulfur (S), CR b R c Or a combination thereof, wherein each of R a to R c is independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group , A halogen atom, a halogen-containing group, or a combination thereof.
For example, when c is 1 in Formula 1, at least one of A 1 , A 2 and A 3 is substituted with 1 or 2 or more methoxy groups (-OCH 3 ) or ethoxy groups (-OC 2 H 5 ) Aromatic ring group. For example, when a, b, and c are 1 in Formula 1, at least one of A 4 and A 5 is a methoxy group (-OCH 3 ) or ethoxy group (-OC 2 H 5 ) Substituted aromatic ring group.
The monomer may have a molecular weight of about 800 to 5,000. By having a molecular weight in the above range, the monomer having a high carbon content has a good solubility in a solvent, and a good thin film by spin-on coating can be obtained.
Hereinafter, the polymer according to another embodiment will be described.
The polymer according to another embodiment may have a repeating unit structure represented by the following formula (2).
(2)
In Formula 2,
A 1 , A 2 , A 3 , A 4 and A 5 are each independently a substituted or unsubstituted aromatic ring group,
X 1 , X 2 , X 3 and X 4 each independently represent a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, an oxygen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group , A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group, A substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof,
Each of C 1 , C 2 , C 3 , C 4 , D 1 , D 2 , D 3 , D 4 , E 1 , E 2 , E 3 and E 4 independently represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted amino group , A halogen atom, an oxygen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkenyl group , A substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, A substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof ,
a, b and c are each independently 0 or 1,
n is an integer of 1 to 500;
For example, in Formula 2, a may be 0, and b and c may be 1.
The polymer has a repeating unit structure in which a quaternary carbon is located between two substituted or unsubstituted aromatic ring groups. The polymer has improved solubility by containing quaternary carbon in the repeating unit, which is advantageous for application to the spin-on coating method.
The polymer may undergo a functional group elimination reaction as shown in Reaction Scheme 1 above at high temperature curing, and the organic film thus prepared may have an excellent film density.
Functional groups represented by the formula (2), with X 1, X 2, X 3 and X 4, and C 1, C 2, C 3, C 4, D 1, D 2, D 3, D 4, E 1, E 2 , E 3 and E 4 can be eliminated or cyclized by high temperature curing of the polymer.
For example, in Formula 2, at least one of X 1 and X 2 may be a hydroxy group, and when a is 0 and b and c are 1, at least one of X 3 and X 4 may be a hydroxy group, But is not limited thereto.
For example, in Formula 2 C 1, D 1 and E at least one of the first is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, wherein the C 2 , At least one of D 2 and E 2 may be a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, wherein a is 0 and b and c is 1 if the C 3, D 3 and E at least one of the three is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, wherein the C 4, D 4 And E 4 may be a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, but is not limited thereto.
On the other hand, the polymer can further improve the corrosion-resisting property by including an aromatic ring group.
For example, in Formula 2, A 1 , A 2 , A 3 , A 4, and A 5 each representing a substituted or unsubstituted aromatic ring group may be independently selected from the groups listed in Group 1.
For example, in formula (2), when a is 0 and b and c are 1, at least one of A 1 , A 2 , A 3 and A 4 is one or more methoxy group (-OCH 3 ) or ethoxy group -OC 2 H 5 ) group.
The polymer may have a weight average molecular weight of about 1,000 to 200,000. By having a weight average molecular weight in the above range, it is possible to optimize by controlling the carbon content of the organic film composition (for example, hard mask composition) containing the polymer and the solubility in solvents.
According to another embodiment, there is provided an organic film composition comprising a solvent, a compound for an organic film which is the above-mentioned monomer, the polymer described above, or a combination thereof.
The solvent is not particularly limited as long as it has sufficient solubility or dispersibility in the organic film compound. Examples of the solvent include propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene glycol butyl ether, tri ) Monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N, N-dimethylformamide, N, Methylpyrrolidinone, acetylacetone, and ethyl 3-ethoxypropionate. The reaction may be carried out in the presence of a base.
The organic film compound may be included in an amount of about 0.1 to 30% 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, a photo acid generator, and a plasticizer.
The surfactant may be, for example, an alkylbenzenesulfonate, an alkylpyridinium salt, a polyethylene glycol, or a quaternary ammonium salt, but is not limited thereto.
Examples of the cross-linking agent include melamine-based, substitution-based, or polymer-based ones. Preferably, the crosslinking agent having at least two crosslinking substituents is, for example, a methoxymethylated glycerol, a butoxymethylated glyceryl, a methoxymethylated melamine, a butoxymethylated melamine, a methoxymethylated benzoguanamine, a 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 photoacid generator may be selected from the group consisting of triphenylsulfonium triflate, triphenylsulfonium antimonate, diphenyliodonium triflate, diphenyliodonium triflate, antimonate, methoxydiphenyliodonium triflate, di-t-butyldiphenyliodonium triflate, 2,6-dinitrobenzylsulfonate (2,6 -dinitrobenzyl sulfonates, pyrogallol tris (alkylsulfonates), N-hydroxysuccinimide triflate, norbornene-dicarboximide-triflate, -dicarboximide-triflate, triphenylsulfonium nonaflate, diphenyliodonium nonaflate, methoxydiphenyliodonium, But are not limited to, methoxydiphenyliodonium nonaflate, di-t-butyldiphenyliodonium nonaflate, N-hydroxysuccinimide nonaflate, norbornene-dicar Triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluorooctanesulfonate, Diphenyliodonium PFOS, methoxydiphenyliodonium PFOS, di-t-butyldiphenyliodonium triflate, N-hydroxysuccinimide PFOS (N -hydroxysuccinimide PFOS, norbornene-dicarboximide PFOS, or a combination thereof, but is not limited thereto.
Examples of the plasticizer include dioctyl phthalate (DOP), dioctyl adipate (DOA), tricresyl phosphate (TCP), diisocctyl phthalate (DIOP), diethonyl phthalate (DL79P), diisononyl phthalate (DINP), diunedicyl phthalate di-2-ethyl hexyl adipate (DIDA), di-2-ethylhexyl sebacate (DOZ), diisooctyl azelate (DIOZ) 2 ethylhexyl phosphate), triphenyl phosphate (TTP), cresyldephenyl phosphate (CDP), tricresyl phosphate (TCP), trixylyl phosphate (TXP), tri-2-ethylhexyl trimellitate (TOTM), polyethylene gpycol ester, alkylsulphonic acid phenyl ester (Triethylene glycol dihexanoate), 4G7 (tetraethyleneglycol diheptanoate), ATEC (acetyl triethyl citrate), TBC (tributyl citrate), TOC (trioctyl citrate), ATOC (acetyl trioctyl citrate), ATHC ), Dimethyl adipate (DMAD), monomethyl adipate (MMAD), dibutyl maleate (DBM), diisobutyl maleate (DIBM) 2-dinitropropyl) formal, TNEN (2,2,2-trinitroethyl 2-nitroxyethyl ether), polyethylene glycol, polypropylene, or combinations thereof.
The additive may be included in an amount of about 0.001 to 40 parts by weight based on 100 parts by weight of the organic film composition. By including it in the above range, the solubility can be improved without changing the optical properties of the organic film composition.
According to another embodiment, there is provided an organic film produced using the organic film composition described above. The organic layer may be in the form of a hardened layer, for example, a hard mask layer, a planarization layer, a sacrificial layer, a filler, etc., and an organic thin film used for electronic devices, .
Hereinafter, a method of forming a pattern using the organic film composition described above will be described.
The method of forming a pattern according to one embodiment includes the steps of providing a material layer on a substrate, applying the organic film composition described above on the material layer, curing the organic film composition to form a hard mask layer, Forming a silicon-containing thin film layer on the silicon-containing thin film layer, forming a photoresist layer on the silicon-containing thin film layer, exposing and developing the photoresist layer to form a photoresist pattern, Selectively removing the thin film layer and the hard mask layer and exposing a portion of the material layer, and etching the exposed portion of the material layer.
The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate.
The material layer is a material to be finally patterned and may be a metal layer such as aluminum, copper, or the like, a semiconductor layer such as silicon, or an insulating layer such as silicon oxide, silicon nitride, or the like. The material layer may be formed by, for example, a chemical vapor deposition method.
The organic film composition is as described above, and may be prepared in a solution form and applied by a spin-on coating method. At this time, the coating thickness of the organic film composition is not particularly limited, but may be applied to a thickness of about 50 to 10,000 ANGSTROM.
The step of curing the organic film composition may include the step of applying energy such as thermal energy, light energy and the like. If the energy applied is, for example, thermal energy, the curing step may include a heat treatment at, for example, about 100 to 500 DEG C for about 10 seconds to 1 hour.
The silicon-containing thin film layer may be formed of, for example, SiCN, SiOC, SiON, SiOCN, SiC, SiN, or a combination thereof.
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
Substituent introduction reaction
To the flask was added naphthalene-2.6-dicarbonyldichloride (34 g, 0.1345 mol), methoxypyrene (62.4 g, 0.269 mol) and 496 g of a 1,2-dichloroethane / chloroform mixed solution. Aluminum chloride (35.8 g, 0.269 mol) was slowly added to the solution, followed by stirring at room temperature for 12 hours. When the reaction was completed, methanol was added and the precipitate formed was filtered and dried.
Addition reaction
Benzyl magnesium chloride (2.0 M in THF) (20 ml, 40 moles) was added slowly at 0 ° C to the flask, and the temperature was gradually raised to room temperature. To the flask was added the compound (6.4 g, 10 mmol) obtained in the above reaction and 285 g of tetrahydrofuran And the mixture was stirred for 24 hours. After the reaction was completed, the reaction mixture was neutralized to pH 7 with 5% hydrochloric acid solution, extracted with ethyl acetate, and dried to obtain a compound represented by the following formula (A).
(A)
Synthetic example 2
Substituent introduction reaction
28 g (0.1 mol) of benzoperylene, 6-methoxy-2-naphthoyl chloride The reaction was carried out in the same manner as in Synthesis Example 1 using 46 g (0.21 mol) of 6-methoxy-2-naphthoyl chloride, 29 g (0.22 mol) of aluminum chloride and 707 g of dichloromethane.
Addition reaction
Using the compound obtained in the above reaction (6.4 g, 10 mmol) and isopropylmagnesium chloride (2.0 M in THF) (12.5 ml, 25 mmol), the compound represented by the formula (B) was obtained in the same manner as in Synthesis Example 1.
[Chemical Formula B]
Synthetic example 3
Substituent introduction reaction
The flask was charged with terephthaloyl dichloride (20.2 g, 0.1 mol), 4-methoxypyrene (11.6 g, 0.05 mol), methoxynaphthalene (7.9 g, 0.05 mol) and 157 g 1,2-dichloroethane. Aluminum chloride (13.2 g, 0.1 mol) was slowly added to the solution and stirred at room temperature. 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 1,200 to 1,500. When the reaction was completed, methanol was added, and the resulting precipitate was filtered, and the remaining monomer was removed using water and methanol to obtain a polymer (Mw: 1500) represented by the following formula (C).
≪ RTI ID = 0.0 &
adding Reaction Reaction
After adding 7 g of the compound obtained in the above reaction and 285 g of tetrahydrofuran to the flask, benzyl magnesium chloride (2.0 M in THF) (20 ml, 40 mol) was added slowly at 0 ° C, the temperature was raised to room temperature, Respectively. After the reaction was completed, the reaction mixture was neutralized to pH 7 with 5% hydrochloric acid solution, extracted with ethyl acetate, and dried to obtain a compound represented by the following formula (D).
[Chemical Formula D]
Synthetic example 4
Substituent introduction reaction
In a 1 L three-necked flask, 21.24 g (0.105 mol) of pyrene and 17.06 g (0.1 mol) of methoxybenzoyl chloride were added with 370 g of dichloromethane, stirred using a stirring bar, and trichloroaluminum 14.67 g (0.11 mol) was added thereto at room temperature little by little. After stirring for 1 hour, 10.15 g (0.05 mol) of terephthaloyl chloride was added, and 29.33 g (0.22 mol) of trichloroaluminum was added thereto little by little with stirring. At this time, the reaction is carried out in an ice bath for 3 hours to control the heat. After completion of the reaction, the reaction product was charged into water, and the reactant (compound represented by the following formula E) obtained by the powder was filtered and dried.
(E)
adding Reaction Reaction
After adding 8.6 g of the compound obtained in the above reaction and 285 g of tetrahydrofuran to the flask, isopropyl magnesium chloride (2.0 M in THF) (20 ml, 40 mol) was slowly added at 0 ° C, Lt; / RTI > After the reaction was completed, the reaction mixture was neutralized to about pH 7 with 5% hydrochloric acid solution, extracted with ethyl acetate, and dried to obtain a compound represented by Formula F below.
[Chemical Formula F]
Comparative Synthetic Example One
9,9-bis (4-methoxyphenyl) -9H-fluorene (21.6 g, 0.057 mol) was added to a 500 ml flask equipped with a thermometer, a condenser and a mechanical stirrer. mol) and 9.6 g (0.057 mol) of 1,4-bis (methoxymethyl) benzene were sequentially added and dissolved in 51 g of propylene glycol monomethyl ether acetate (PGMEA). Thereafter, 0.15 g (0.001 mol) of diethylsulfite was added thereto, followed by stirring at 90 to 120 ° C for about 5 to 10 hours. A sample was taken at intervals of 1 hour from the polymerization reaction product thus obtained, 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 and then cooling to room temperature, the reaction product was poured into 40 g of distilled water and 400 g of methanol, stirred vigorously and allowed to stand. The supernatant was removed and the precipitate was dissolved in 80 g of PGMEA (PGMEA), and then 40 g of metalol and 40 g of water were stirred vigorously (1 st). The resulting supernatant was again removed and the precipitate was dissolved in 40 g of propylene glycol monomethyl ether acetate (PGMEA) (second order). The primary and secondary processes were referred to as a one-time purification process, and this purification process was performed three times in total. The purified polymer was dissolved in 80 g of propylene glycol monomethyl ether acetate (PGMEA), and methanol and distilled water remaining in the solution were removed under reduced pressure to obtain a polymer represented by the following formula (G) (weight average molecular weight (Mw) = 2500 ).
[Formula G]
Comparative Synthetic Example 2
28.43 g (0.2 mol) of 4,4'-bis (methoxymethyl) biphenyl, 28.83 g (0.2 mol) of naphthalen-1-ol, , 53 g of propylene glycol monomethyl ether acetate (PGMEA) and 1.23 g (8 mmol) of diethylsulfate were used to obtain a polymer represented by the following formula (H) Molecular weight (Mw) = 4300).
[Formula H] <
Hard mask Preparation of composition
Example One
The compound obtained in Synthesis Example 1 was dissolved in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (7: 3 (v / v)), . The compound was adjusted according to the thickness desired.
Example 2
A hard mask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 2 was used instead of the compound obtained in Synthesis Example 1.
Example 3
A hard mask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 3 was used instead of the compound obtained in Synthesis Example 1.
Example 4
A hard mask composition was prepared in the same manner as in Example 1, except that the compound obtained in Synthesis Example 4 was used instead of the compound obtained in Synthesis Example 1.
Comparative Example One
A hard mask composition was prepared in the same manner as in Example 1, except that the compound obtained in Comparative Synthesis Example 1 was used instead of the compound obtained in Synthesis Example 1.
Comparative Example 2
A hard mask composition was prepared in the same manner as in Example 1, except that the compound obtained in Comparative Synthesis Example 2 was used instead of the compound obtained in Synthesis Example 1.
evaluation
Rating 1: Awareness of corrosion
The hard mask composition (compound content: 12 to 15% by weight) according to Examples 1 to 4 and Comparative Examples 1 and 2 was spin-on coated on a silicon wafer to a thickness of 4,000 Å and then heat-treated at 400 ° C. for 2 minutes on a hot plate To form a thin film.
The thickness of the thin film was then measured. Subsequently, the thin film was dry-etched for 100 seconds and 60 seconds using CHF 3 / CF 4 mixed gas and N 2 / O 2 mixed gas, respectively, and then the thickness of the thin film was measured again. The bulk etch rate (BER) was calculated from the thickness and etch time of the thin film before and after dry etching according to the following equation.
[Equation 1]
(Initial thin film thickness - thin film thickness after etching) / etching time (Å / s)
The results are shown in Table 1.
Referring to Table 1, the thin films formed from the hard mask compositions according to Examples 1 to 4 had sufficient erosion resistance to the etching gas as compared with the thin films formed from the hard mask composition according to Comparative Examples 1 and 2, thereby improving bulk etch characteristics can confirm.
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 (26)
menstruum
Containing
Organic film composition:
[Chemical Formula 1]
In Formula 1,
A 1 , A 2 , A 3 , A 4 and A 5 are each independently a substituted or unsubstituted aromatic ring group,
X 1 , X 2 , X 3 and X 4 each independently represent a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, an oxygen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group , A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group, A substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof,
Each of C 1 , C 2 , C 3 , C 4 , D 1 , D 2 , D 3 , D 4 , E 1 , E 2 , E 3 and E 4 independently represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted amino group , A halogen atom, an oxygen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkenyl group , A substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, A substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof ,
a, b and c are each independently 0 or 1;
Wherein A 1 , A 2 , A 3 , A 4 and A 5 are each independently a substituted or unsubstituted aromatic ring group selected from the groups listed in the following group 1:
[Group 1]
In the group 1,
Z 1 represents 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, a substituted or unsubstituted C2 to C20 heteroaryl (O), sulfur (S), or a combination thereof, wherein R is a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, a is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, a halogen atom,
Z 3 to Z 18 are each independently C═O, NR a , oxygen (O), sulfur (S), CR b R c or combinations thereof wherein R a to R c are each independently hydrogen, A substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, a halogen atom, a halogen-containing group, or a combination thereof.
Wherein at least one of X 1 and X 2 is a hydroxy group.
Wherein a, b and c are 1, and at least one of X 3 and X 4 is a hydroxy group.
Wherein a is 0, b and c are 1, and at least one of X 3 and X 4 is a hydroxy group.
The C 1, D 1 and E at least one substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, wherein the C 2, D 2 and E 2 of one of the At least one of which is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.
Wherein a, b and c are 1, and at least one of C 3 , D 3 and E 3 is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, Wherein at least one of C 4 , D 4 and E 4 is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.
Wherein c is 1 and at least one of A 1 , A 2 and A 3 is an aromatic ring group substituted with one or more methoxy groups (-OCH 3 ) or ethoxy group (-OC 2 H 5 ) groups.
Wherein the a, b and c are 1 and at least one of A 4 and A 5 is an aromatic ring group substituted with one or more methoxy group (-OCH 3 ) or ethoxy group (-OC 2 H 5 ) .
Wherein the monomer has a molecular weight of 800 to 5,000.
menstruum
Containing
Organic film composition:
(2)
In Formula 2,
A 1 , A 2 , A 3 , A 4 and A 5 are each independently a substituted or unsubstituted aromatic ring group,
X 1 , X 2 , X 3 and X 4 each independently represent a hydroxyl group, a substituted or unsubstituted amino group, a halogen atom, an oxygen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group , A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group, A substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof,
Each of C 1 , C 2 , C 3 , C 4 , D 1 , D 2 , D 3 , D 4 , E 1 , E 2 , E 3 and E 4 independently represents a hydrogen atom, a hydroxyl group, a substituted or unsubstituted amino group , A halogen atom, an oxygen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkenyl group , A substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, A substituted or unsubstituted C1 to C4 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, or a combination thereof ,
a, b and c are each independently 0 or 1,
n is an integer of 1 to 500;
Wherein A 1 , A 2 , A 3 , A 4 and A 5 are each independently a substituted or unsubstituted aromatic ring group selected from the groups listed in the following group 1:
[Group 1]
In the group 1,
Z 1 represents 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, a substituted or unsubstituted C2 to C20 heteroaryl (O), sulfur (S), or a combination thereof, wherein R is a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, a is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, a halogen atom,
Z 3 to Z 18 are each independently C═O, NR a , oxygen (O), sulfur (S), CR b R c or combinations thereof wherein R a to R c are each independently hydrogen, A substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, a halogen atom, a halogen-containing group, or a combination thereof.
Wherein at least one of X 1 and X 2 is a hydroxy group.
a is 0, b and c are 1, and at least one of X 3 and X 4 is a hydroxy group.
The C 1, D 1 and E at least one substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof, wherein the C 2, D 2 and E 2 of one of the At least one of which is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.
a is 0, b and c are 1, and at least one of C 3 , D 3 and E 3 is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, , At least one of C 4 , D 4 and E 4 is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.
a is 0, b and c are 1, and at least one of A 1 , A 2 , A 3 and A 4 is substituted with one or more methoxy group (-OCH 3 ) or ethoxy group (-OC 2 H 5 ) Wherein the aromatic ring group is an aromatic ring group.
Wherein the polymer has a weight average molecular weight of 1,000 to 200,000.
Wherein the monomer is contained in an amount of 0.1 wt% to 30 wt% based on the total amount of the organic film composition.
Wherein the organic film comprises a hard mask layer.
Applying the organic film composition according to any one of claims 1 to 18 to the material layer,
Curing 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.
Wherein the silicon-containing thin film layer comprises SiCN, SiOC, SiON, SiOCN, SiC, SiN, or a combination thereof.
Further comprising forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist layer.
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