Hardmask composition, hardmask layer and method of forming pattern
阅读说明：本技术 硬掩模组合物、硬掩模层以及形成图案的方法 (Hardmask composition, hardmask layer and method of forming pattern ) 是由 金昇炫 郑铉日 金尙美 金铃根 朴相喆 于 2020-10-13 设计创作，主要内容包括：本发明提供一种硬掩模组合物、硬掩模层以及形成图案的方法,所述硬掩模组合物包含聚合物和溶剂,所述聚合物包含由化学式1表示的结构单元。在化学式1中,A、B以及R1到R5的定义如本说明书中所描述。所述硬掩模组合物能够改进耐蚀刻性和膜密度。[化学式1](The present invention provides a hard mask composition, a hard mask layer, and a method of forming a pattern, the hard mask composition including a polymer including a structural unit represented by chemical formula 1 and a solvent. In chemical formula 1, A, B and the definitions of R1 to R5 are as described in the specification. The hardmask composition can improve etch resistance and film density. [ chemical formula 1])
1. A hardmask composition comprising:
a polymer comprising a structural unit represented by chemical formula 1, and
solvent:
[ chemical formula 1]
Wherein, in chemical formula 1,
a is a substituted or unsubstituted pyrenylene group,
b is hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, halogen, nitro, amino, hydroxy, or combinations thereof,
R1to R5Independently is hydrogen, deuterium, hydroxyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 heteroalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heterocyclyl, or a combination thereof, and
R1to R5Is independently hydroxy, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof.
2. The hardmask composition according to claim 1, wherein
A is an unsubstituted pyrenylene group, or
Pyrenylene substituted with at least one substituent,
wherein the substituents are independently deuterium, hydroxyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 heteroalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heterocyclyl, or a combination thereof.
3. The hardmask composition according to claim 1, wherein a is an unsubstituted pyrenylene or a pyrenylene substituted with at least one hydroxyl group.
4. The hardmask composition according to claim 1, wherein R1To R5Two or three of (a) are independently hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof.
5. The hardmask composition according to claim 1, wherein
R3And R4Independently is hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof;
R3and R5Independently is hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof; or
R1、R3And R5Independently is hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof.
6. The hardmask composition according to claim 1, wherein the structural unit represented by chemical formula 1 is represented by one of chemical formulae 2 to 4:
[ chemical formula 2]
[ chemical formula 3]
[ chemical formula 4]
Wherein, in chemical formulas 2 to 4,
b is hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, halogen, nitro, amino, hydroxy, or combinations thereof,
R1、R3、R4and R5Independently is hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof, and
R6is hydrogen, hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof.
7. The hardmask composition according to claim 1, wherein
The structural unit represented by chemical formula 1 is derived from a reaction mixture comprising:
substituted or unsubstituted pyrene, and
benzaldehyde substituted by at least two substituents,
wherein the substituents may independently be hydroxyl, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof.
8. The hardmask composition according to claim 7, wherein the substituted or unsubstituted pyrene is pyrene or hydroxypyrene.
9. The hardmask composition according to claim 7, wherein the benzaldehyde substituted with at least two substituents is a dihydroxybenzaldehyde, a hydroxymethoxybenzaldehyde, a hydroxyethoxybenzaldehyde, a hydroxypropoxybenzaldehyde, a hydroxybutyloxybenzaldehyde, a trihydroxybenzaldehyde, or a combination thereof.
10. A hardmask layer comprising a cured product of the hardmask composition according to any one of claims 1 to 9.
11. A method of forming a pattern comprising
Coating the hardmask composition according to any one of claims 1 to 9 on a material layer and heat-treating the resultant to form a hardmask layer,
a photoresist layer is formed on the hard mask layer,
exposing and developing the photoresist layer to form a photoresist pattern,
selectively removing the hard mask layer using the photoresist pattern to expose a portion of the material layer, an
The exposed portions of the material layer are etched.
Technical Field
A hardmask composition, a hardmask layer comprising a cured product of the hardmask composition, and a method of forming a pattern using the hardmask composition are disclosed.
Background
Recently, the semiconductor industry has developed ultra-fine technology of patterns having a size of several nanometers to several tens of nanometers. Such hyperfine techniques mainly require effective photolithography techniques.
Typical lithographic techniques include: providing a material layer on a semiconductor substrate; coating a photoresist layer on the material layer; exposing and developing the photoresist layer to provide a photoresist pattern; and etching the material layer using the photoresist pattern as a mask.
Today, it is difficult to provide a fine pattern having an excellent profile only by the above-mentioned typical photolithography technique according to the small size of a pattern to be formed. Accordingly, an auxiliary layer called a hard mask layer may be formed between the material layer and the photoresist layer to provide a fine pattern.
Disclosure of Invention
Embodiments provide a hardmask composition capable of improving etch resistance.
Another embodiment provides a hardmask layer comprising a cured product of the hardmask composition.
Another embodiment provides a method of forming a pattern using a hardmask composition.
According to an embodiment, a hardmask composition including a polymer including a structural unit represented by chemical formula 1 and a solvent is provided.
[ chemical formula 1]
In the chemical formula 1, the first and second,
a is a substituted or unsubstituted pyrenylene group,
b is hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, halogen, nitro, amino, hydroxy, or combinations thereof,
R1to R5Independently is hydrogen, deuterium, hydroxyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 heteroalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heterocyclyl, or a combination thereof, and
R1to R5Is independently hydroxy, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof.
A may be an unsubstituted pyrenylene group or a pyrenylene group substituted with at least one substituent group, wherein the substituent groups may independently be deuterium, a hydroxyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, or a combination thereof.
A may be an unsubstituted pyrenylene group or a pyrenylene group substituted with at least one hydroxyl group.
R1To R5Two or three of (a) can be independently hydroxyl, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof.
R3And R4May independently be hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or combinations thereof;
R3and R5May independently be hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or combinations thereof; or
R1、R3And R5Can be independently hydroxyl, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or combinations thereof.
The structural unit represented by chemical formula 1 may be represented by one of chemical formulas 2 to 4.
[ chemical formula 2]
[ chemical formula 3]
[ chemical formula 4]
In the chemical formulae 2 to 4,
b is hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, halogen, nitro, amino, hydroxy, or combinations thereof,
R1、R3、R4and R5Independently is hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof, and
R6is hydrogen, hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxyUnsubstituted butoxy, or combinations thereof.
The structural unit represented by chemical formula 1 may be derived from the following reaction mixture: substituted or unsubstituted pyrene (pyrene), and
benzaldehyde substituted with at least two substituents, wherein the substituents may independently be hydroxyl, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof.
The substituted or unsubstituted pyrene may be pyrene or hydroxypyrene.
The benzaldehyde substituted with at least two substituents is dihydroxybenzaldehyde, hydroxymethoxybenzaldehyde, hydroxyethoxybenzaldehyde, hydroxypropoxybenzaldehyde, hydroxybutyoxybenzaldehyde, trihydroxybenzaldehyde or a combination thereof.
According to another embodiment, a hardmask layer comprising a cured product of a hardmask composition is provided.
According to another embodiment, a method of forming a pattern includes: the method includes coating a hard mask composition on a material layer and heat-treating the resultant to form a hard mask layer, forming a photoresist layer on the hard mask layer, exposing and developing the photoresist layer to form a photoresist pattern, selectively removing the hard mask layer using the photoresist pattern to expose a portion of the material layer, and etching the exposed portion of the material layer.
The solubility of the polymer and the etching resistance and film density of the hard mask layer can be simultaneously ensured.
Detailed Description
Hereinafter, example embodiments of the present disclosure will be described in detail, and can be easily performed by those skilled in the art. This disclosure may, however, be embodied in many different forms and should not be construed as limited to the example embodiments set forth herein.
As used herein, "substituted," when a definition is not otherwise provided, refers to replacement of a hydrogen atom of a compound by a substituent selected from: deuterium, a halogen atom (F, Br, Cl, or I), a hydroxyl group, a nitro group, a cyano group, an amino group, an azide group, an amidino group, a hydrazine group, a hydrazono group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C6 to C30 aryl group, a C7 to C30 aralkyl group, a C1 to C30 alkoxy group, a C1 to C30 heteroalkyl group, a C3 to C30 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocyclic group, and a combination thereof.
In addition, two adjacent substituents of a substituted halogen atom (F, Br, Cl, or I), a hydroxyl group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazine group, a hydrazono group, a carbonyl group, a carbamoyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C6 to C30 aryl group, a C7 to C30 aralkyl group, a C1 to C30 alkoxy group, a C1 to C30 heteroalkyl group, a C3 to C30 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C84 6 to C4656 cycloalkynyl group, and a C2 to C. For example, a substituted C6-C30 aryl group may be fused with another adjacent substituted C6-C30 aryl group to form a substituted or unsubstituted fluorene ring.
As used herein, "hetero" refers to a group containing 1 to 3 heteroatoms selected from N, O, S, Se and P, when no definition is otherwise provided.
As used herein, "aryl" refers to a group comprising at least one hydrocarbon aromatic moiety, and includes hydrocarbon aromatic moieties linked by single bonds and hydrocarbon aromatic moieties fused, directly or indirectly, to provide non-aromatic fused rings. The aryl group can comprise a monocyclic, polycyclic, or fused polycyclic (i.e., rings that share adjacent pairs of carbon atoms) functional group.
As used herein, "heterocyclyl" is a concept that includes heteroaryl and may include at least one heteroatom selected from N, O, S, P and Si, rather than carbon (C) in cyclic compounds such as aryl, cycloalkyl, fused rings thereof, or combinations thereof. When the heterocyclyl is a fused ring, all or each ring of the heterocyclyl may contain one or more heteroatoms.
More specifically, the substituted or unsubstituted aryl group can be substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl (naphthyl group), substituted or unsubstituted anthryl (anthryl group), substituted or unsubstituted phenanthryl (phenanthryl group), substituted or unsubstituted condensed tetraphenyl (naphthyl group), substituted or unsubstituted pyrenyl (pyrenyl group), substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted chrysenyl (chrysenyl group), substituted or unsubstituted terphenyl, substituted or unsubstituted perylene (perylenyl group), substituted or unsubstituted indenyl (indenylgroup), substituted or unsubstituted fluorenyl (fluorenyl group), combinations thereof, or combinations thereof, but is not limited thereto.
More specifically, the substituted or unsubstituted heterocyclic group may be a substituted or unsubstituted furyl (furyl group), substituted or unsubstituted thienyl (thiophenyl group), substituted or unsubstituted pyrrolyl (pyrroliyl group), substituted or unsubstituted pyrazolyl (pyrazolyl group), substituted or unsubstituted imidazolyl (imidazolyl group), substituted or unsubstituted triazolyl (triazolyl group), substituted or unsubstituted oxazolyl (oxazolyl group), substituted or unsubstituted thiazolyl (thiazolyl group), substituted or unsubstituted oxadiazolyl (oxadiazolyl group), substituted or unsubstituted thiadiazolyl (thiadiazolyl group), substituted or unsubstituted pyridyl (pyridyl group), substituted or unsubstituted pyrimidyl (pyrimidyl group), substituted or unsubstituted pyrazinyl (pyrazinyl group) or unsubstituted pyridyl (pyridyl group), substituted or unsubstituted pyrimidyl (pyrimidyl group), substituted or unsubstituted pyrrolyl (pyridyl group), substituted or unsubstituted pyrrolyl group (pyridyl group, substituted or unsubstituted pyridyl group (pyridyl group), substituted or unsubstituted pyridyl group (pyridyl group, substituted or substituted pyridyl group (pyridyl group, substituted or unsubstituted triazinyl (triazinyl group), substituted or unsubstituted benzofuranyl group, substituted or unsubstituted benzothienyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted indolyl (indolyl group), substituted or unsubstituted quinolyl group, substituted or unsubstituted isoquinolyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted benzoxazinyl group, substituted or unsubstituted benzothiazinyl (benzothiazinyl group), substituted or unsubstituted acridinyl group, substituted or unsubstituted oxazinyl group, substituted or unsubstituted azinyl group, substituted or unsubstituted acridinyl group, substituted or unsubstituted oxazinyl group, substituted or unsubstituted thiazinyl group, substituted or unsubstituted oxazinyl group, benzoxazinyl group, substituted or unsubstituted oxazinyl group (phenazinyl group, substituted or unsubstituted oxazinyl group, benzoxazinyl group, substituted or substituted, Substituted or unsubstituted phenoxazinyl (phenoxazinyl group), substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl (dibenzothiophenyl group), substituted or unsubstituted carbazolyl (carbazolyl group), substituted or unsubstituted pyridoindolyl (pyridoindoxyl group), substituted or unsubstituted benzopyridoxazinyl (benzopyridoxazinyl group), substituted or unsubstituted benzopyridothiazinyl (benzopyridoxazinyl group), substituted or unsubstituted 9,9-dimethyl 9,10dihydroacridinyl (9,9-dimethyl 9,10dihydroacridinyl group), combinations thereof or fused rings of the foregoing, but are not limited thereto. In one embodiment of the invention, the heterocyclyl or heteroaryl group can be pyrrolyl, indolyl, or carbazolyl.
As used herein, polymer is meant to include oligomers and polymers.
Hereinafter, the hardmask composition according to the embodiment is described.
The hardmask composition according to an embodiment includes a polymer and a solvent.
The polymer may include a backbone comprising an aromatic ring and a side chain comprising an aromatic ring bonded to the backbone and substituted with at least two substituents.
The backbone comprising an aromatic ring may comprise a condensed aromatic ring, and may comprise, for example, a substituted or unsubstituted pyrene. The side chain comprising an aromatic ring substituted with at least two substituents may comprise benzene substituted with at least two substituents. Herein, the substituent may be a hydrophilic functional group, for example, a hydroxyl group, a substituted or unsubstituted alkoxy group.
Therefore, by including an aromatic ring having a high carbon content in the main chain, a hard film-like polymer layer can be formed, thereby improving etching resistance, and by including an aromatic ring having a hydrophilic functional group in the side chain, solubility to a solvent can be improved.
For example, the polymer may include a structural unit represented by chemical formula 1.
[ chemical formula 1]
In the chemical formula 1, the first and second,
a is a substituted or unsubstituted pyrenylene group,
b is hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, halogen, nitro, amino, hydroxy, or combinations thereof,
R1to R5Is the same or different and is independently hydrogen, deuterium, hydroxyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 heteroalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heterocyclyl, or a combination thereof, and
R1to R5Is independently hydroxy, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof.
For example, a may be an unsubstituted pyrenylene or a pyrenylene substituted with the same or different at least one substituent, wherein the substituents may independently be deuterium, hydroxyl, substituted or unsubstituted C1 to C30 alkoxy, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heterocyclyl, or a combination thereof.
For example, in a, when the number of substituents is plural, all the substituents may be substituted by the same ring among rings in pyrene, or may be substituted by different rings among rings in pyrene.
For example, a may be an unsubstituted pyrenylene group, a pyrenylene group substituted with one substituent group, or a pyrenylene group substituted with two substituent groups.
For example, a may be an unsubstituted pyrenylene group, a pyrenylene group substituted with at least one hydroxyl group, or a pyrenylene group substituted with at least one C1 to C30 alkoxy group. Herein, the C1-C30 alkoxy group may be a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted propoxy group, a substituted or unsubstituted butoxy group, or a combination thereof.
For example, a may be an unsubstituted pyrenylene group, a pyrenylene group substituted with one or two hydroxyl groups, and for example, a may be a pyrenylene group, a 1-hydroxypyrenylene group or a 2-hydroxypyrenylene group, but is not limited thereto.
As described above, the polymer may comprise benzene substituted with at least two hydrophilic functional groups in the side chains, and the benzene substituted with at least two hydrophilic functional groups in the side chains and the substituted or unsubstituted pyrenylene in the main chain may be bonded to a tertiary or quaternary carbon. Thus, the polymer may have increased solubility to a solvent and may be effectively applied to a solution process, such as spin coating, and may have a p-N2/O2Improved etch resistance of the mixed gas and providing a polymer layer with improved film density.
For example, R1To R5May be the same or different and may independently be hydrogen, deuterium, hydroxy, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof. Specifically, R1To R5May be the same or different and may independently be hydrogen, deuterium, hydroxyl, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof.
For example, R1To R52 to 5 of which may be independently hydroxy, substituted or unsubstituted C1 to C30 alkoxyOr a combination thereof, and for example, R1To R52 or 3 of (a) may be independently hydroxyl, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof.
For example, R3May be hydroxyl, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof, and is desirably hydroxyl.
For example, R3And R4May be the same or different and may independently be hydroxy, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof;
R3and R5May be the same or different and may independently be hydroxy, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof; or
R1、R3And R5May be the same or different and may independently be hydroxyl, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof.
For example, R3May be hydroxy, R4May be hydroxy or substituted or unsubstituted C1 to C30 alkoxy; r3And R5May be a hydroxyl group; or R1、R3And R5May be a hydroxyl group.
For example, R1To R5At least two of which can be independently hydroxyl, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof.
For example, R1To R5Two to five of which can be independently hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or combinations thereof, e.g., R1To R52 or 3 of can be independently hydroxyl, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof.
For example, R3Can beA hydroxyl group, a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted propoxy group, a substituted or unsubstituted butoxy group, or a combination thereof, and desirably is a hydroxyl group.
For example, R3And R4May be the same or different and may independently be hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof;
R3and R5May be the same or different and may independently be hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof; or
R1、R3And R5May be the same or different and may independently be hydroxyl, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or a combination thereof.
For example, R3May be hydroxy, R4Can be hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, or substituted or unsubstituted butoxy; r3And R5May be a hydroxyl group; or R1、R3And R5May be a hydroxyl group.
For example, R2May be hydrogen.
The structural unit represented by chemical formula 1 may be represented by one of chemical formulas 2 to 4.
[ chemical formula 2]
[ chemical formula 3]
[ chemical formula 4]
In the chemical formulae 2 to 4,
B、R1、R3、R4and R5Is the same as described above, and
R6is hydrogen, hydroxy, substituted or unsubstituted C1 to C30 alkoxy, or a combination thereof.
For example, R6Can be hydrogen, hydroxy, substituted or unsubstituted methoxy, substituted or unsubstituted ethoxy, substituted or unsubstituted propoxy, substituted or unsubstituted butoxy, or combinations thereof.
For example, the structural unit represented by chemical formula 1 may be derived from a reaction mixture including substituted or unsubstituted pyrene and benzaldehyde substituted with at least two substituents. Herein, the substituents may independently be deuterium, hydroxyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 heteroalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heterocyclyl, or a combination thereof, and desirably are independently hydroxyl, substituted or unsubstituted C1-C30 alkoxy, or a combination thereof.
The structural unit may be obtained by condensation reaction of a reaction mixture, but is not limited thereto.
For example, a substituted or unsubstituted pyrene may be an unsubstituted pyrene or a pyrene substituted with at least one substituent which is the same as or different from each other. Herein, when the number of the substituents is plural, all the substituents may be substituted by the same ring among rings in pyrene, or may be substituted by different rings among rings in pyrene.
For example, a substituted or unsubstituted pyrene can be an unsubstituted pyrene, a pyrene substituted with one substituent, or a pyrene substituted with two substituents.
For example, the substituted or unsubstituted pyrene can be unsubstituted pyrene, pyrene substituted with at least one hydroxyl group, pyrene substituted with at least one C1 to C30 alkoxy group, or a combination thereof. Herein, the C1-C30 alkoxy group may be a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted propoxy group, a substituted or unsubstituted butoxy group, or a combination thereof.
For example, substituted or unsubstituted pyrene may be pyrene or pyrene substituted with one or two hydroxyl groups, such as, but not limited to, pyrene, 1-hydroxypyrene or 2-hydroxypyrene.
For example, the benzaldehyde substituted with at least two substituents may be a benzaldehyde substituted with 2 to 5 substituents which may be the same as or different from each other, for example, a benzaldehyde substituted with 2 or 3 substituents.
For example, the benzaldehyde substituted with at least two substituents may be a benzaldehyde substituted with at least two hydroxyl groups, a benzaldehyde substituted with at least two C1 to C30 alkoxy groups, and a benzaldehyde substituted with at least one hydroxyl group and at least one C1 to C30 alkoxy group, or a combination thereof. For example, the benzaldehyde substituted with at least two substituents may be benzaldehyde substituted with two hydroxyl groups, benzaldehyde substituted with three hydroxyl groups, benzaldehyde substituted with two C1 to C30 alkoxy groups, benzaldehyde substituted with three C1 to C30 alkoxy groups, benzaldehyde substituted with one hydroxyl group and one C1 to C30 alkoxy group, or a combination thereof. Herein, the C1-C30 alkoxy group may be a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, a substituted or unsubstituted propoxy group, a substituted or unsubstituted butoxy group, or a combination thereof.
For example, the benzaldehyde substituted with at least two substituents may be dihydroxybenzaldehyde, hydroxymethoxybenzaldehyde, hydroxyethoxybenzaldehyde, hydroxypropoxybenzaldehyde, hydroxybutyloxybenzaldehyde, trihydroxybenzaldehyde, or a combination thereof.
For example, the benzaldehyde substituted with at least two substituents may be 3, 4-dihydroxybenzaldehyde, 2, 4-dihydroxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde or 2,4, 6-trihydroxybenzaldehyde, but is not limited thereto.
The polymer may include one or more structural units represented by chemical formula 1, and a plurality of structural units represented by chemical formula 1 may be the same as or different from each other.
The polymer may include the structural unit represented by chemical formula 1 as a plurality of repeating units, and the number and arrangement of the repeating units are not limited.
The polymer may further include one or more other structural units in addition to the structural units described above, and the number and arrangement of the structural units are not limited.
The polymer may have a weight average molecular weight of about 500 to about 200,000. More specifically, the polymer may have a weight average molecular weight of about 1,000 to about 100,000, about 1,200 to about 50,000, or about 1,500 to about 10,000. When the polymer has a weight average molecular weight within the range, the polymer can be optimized by adjusting the amount of carbon and solubility in a solvent.
On the other hand, the solvent used in the hardmask composition may be any one having sufficient solubility or dispersibility for the polymer, and may contain, for example, at least one selected from: propylene glycol, propylene glycol diacetate, methoxypropylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N-dimethylformamide, N-dimethylacetamide, methylpyrrolidone, acetylacetone, and ethyl 3-ethoxypropionate, but are not limited thereto.
The polymer may be included in an amount of about 0.1 wt% to about 50 wt%, about 0.5 wt% to about 40 wt%, about 1 wt% to about 30 wt%, or about 3 wt% to about 20 wt%, based on the total amount of the hardmask composition. When the polymer is included in the range, the thickness, surface roughness, and planarization of the hard mask can be controlled.
The hardmask composition may further include additives of surfactants, cross-linking agents, thermal acid generators, or plasticizers.
The surfactant may include, for example, a fluoroalkyl compound, an alkylbenzene sulfonate, an alkylpyridinium salt, a polyethylene glycol, or a quaternary ammonium salt, but is not limited thereto.
The crosslinking agent may be, for example, a melamine-based, substituted urea-based or polymer-based crosslinking agent. Desirably, it may be a crosslinking agent having at least two crosslink forming substituents, for example, a compound such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea (methoxymethylated urea), butoxymethylated urea (butoxymethylated urea), methoxymethylated thiourea or butoxymethylated thiourea, and the like.
The crosslinking agent may be a crosslinking agent having high heat resistance. The crosslinking agent having high heat resistance may be a compound containing a crosslinking substituent group containing an aromatic ring (e.g., a benzene ring or a naphthalene ring) in the molecule.
The thermal acid generator may be, for example, an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate (pyridinium-tolenesulfonate), salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalene carbonic acid, and the like, or/and 2,4,4, 6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, other alkyl organosulfonates, and the like, but is not limited thereto.
The additive may be included in an amount of about 0.001 to 40 parts by weight, about 0.01 to 30 parts by weight, or about 0.1 to 20 parts by weight, based on 100 parts by weight of the hardmask composition. Within the range, the solubility may be improved without changing the optical properties of the hardmask composition.
According to another embodiment, an organic layer produced using the hardmask composition is provided. The organic layer may be formed, for example, by coating a hardmask composition on a substrate and heat-treating it for curing, and may include, for example, a hardmask layer for an electronic device, a planarization layer, a sacrificial layer, a filler, and the like.
According to another embodiment, a hard mask layer comprising a cured product of the foregoing hard mask composition is provided.
For example, the cured product comprises a condensed polycyclic aromatic hydrocarbon.
Since the cured product includes condensed polycyclic aromatic hydrocarbons, it may exhibit high etch resistance that can withstand etching gases and chemical liquids exposed in subsequent processes including etching processes.
Hereinafter, a method of forming a pattern using the foregoing hardmask composition is described.
The method of forming a pattern according to an embodiment includes: the method includes forming a material layer on a substrate, coating a hard mask composition including the aforementioned polymer and solvent on the material layer, heat-treating the hard mask composition to form a hard mask layer, forming a photoresist layer on the hard mask layer, exposing and developing the photoresist layer to form a photoresist pattern, selectively removing the hard mask layer using the photoresist pattern 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 the material that will ultimately be patterned, for example: metal layers such as aluminum and copper layers; a semiconductor layer, such as a silicon layer; or an insulating layer such as a silicon oxide layer and a silicon nitride layer. The material layer may be formed by a method such as a Chemical Vapor Deposition (CVD) process.
The hardmask composition is the same as described above, and may be applied in solution by spin-on coating. Herein, the thickness of the hardmask composition is not particularly limited, but may be, for example, about 50 angstroms to about 200,000 angstroms.
The heat treatment of the hardmask composition may be performed, for example, at about 100 c to about 700 c for about 10 seconds to about 1 hour.
For example, the method may also include forming a silicon-containing thin layer on the hard mask layer. The silicon-containing thin layer may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, SiO, and/or SiN, and the like.
For example, the method may further comprise forming a bottom anti-reflective coating (BARC) layer on an upper surface of the silicon-containing thin layer or on an upper surface of the hard mask layer prior to forming the photoresist layer.
The exposure of the photoresist layer may be performed using, for example, ArF, KrF, or EUV. After exposure, a thermal treatment may be performed at about 100 ℃ to about 700 ℃.
The etching process of the exposed portion of the material layer may be performed by a dry etching process using an etching gas, and the etching gas may be, for example, N2/O2、CHF3、CF4、Cl2、BCl3And mixed gases thereof.
The etched material layer may be formed in a plurality of patterns, and the plurality of patterns may be metal patterns, semiconductor patterns, insulating patterns, and the like, such as different patterns of a semiconductor integrated circuit device.
Hereinafter, embodiments are described in more detail with reference to examples. However, these examples are exemplary, and the scope is not limited thereto.
Synthesis of polymers
Synthesis example 1
1-hydroxypyrene (21.8 g, 0.1 mol) and 3, 4-dihydroxybenzaldehyde (13.8 g, 0.1 mol) were added to a 250 ml flask, and then, a solution prepared by dissolving p-toluenesulfonic acid monohydrate (0.57 g, 0.03 mmol) in 100 g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) was added thereto. The obtained mixture was stirred at 90 ℃ to perform polymerization reaction, and when the weight average molecular weight reached 2,000 to 2,500, the reaction was completed. When the polymerization reaction was completed, the reaction was cooled to room temperature, and then, 300 g of distilled water and 300 g of methanol were added thereto, and then, stirred vigorously and allowed to stand. After removing the supernatant therefrom, the precipitate therein was dissolved in 100 g of PGMEA, 300 g of methanol and 300 g of distilled water were added thereto, and then vigorously stirred and allowed to stand (primary process). After the supernatant was removed again, the precipitate therein was dissolved in 80 g of PGMEA (secondary process). One primary process and one secondary process are considered as one purification process, which is performed three times in total. After three purification processes, the polymer obtained therefrom was dissolved in 80 g of PGMEA, and concentrated under reduced pressure to remove residual methanol and distilled water, obtaining a polymer comprising the structural unit (repeating unit) represented by chemical formula 1 a. (Mw: 2,455)
[ chemical formula 1a ]
Synthesis example 2
A polymer comprising a structural unit (repeating unit) represented by chemical formula 1b was synthesized according to the same method as in synthesis example 1, except that 4-hydroxy-3-methoxybenzaldehyde (15.2 g, 0.1 mol) was used instead of 3, 4-dihydroxybenzaldehyde (13.8 g, 0.1 mol). (Mw: 2,785)
[ chemical formula 1b ]
Synthesis example 3
A polymer comprising a structural unit (repeating unit) represented by chemical formula 1c was synthesized according to the same method as in synthesis example 1, except that 2,4, 6-trihydroxybenzaldehyde (15.4 g, 0.1 mol) was used instead of 3, 4-dihydroxybenzaldehyde (13.8 g, 0.1 mol). (Mw: 2,127)
[ chemical formula 1c ]
Synthesis example 4
A polymer comprising a structural unit (repeating unit) represented by chemical formula 1d was synthesized according to the same method as in synthesis example 1, except that pyrene (20.2 g, 0.1 mol) was used instead of 1-hydroxypyrene (21.8 g, 0.1 mol) and 2, 4-dihydroxybenzaldehyde (13.8 g, 0.1 mol) was used instead of 3, 4-dihydroxybenzaldehyde (13.8 g, 0.1 mol). (Mw: 2,086)
[ chemical formula 1d ]
Synthesis of comparative example 1
A polymer comprising a structural unit (repeating unit) represented by chemical formula a was synthesized according to the same method as in synthesis example 1, except that 4-hydroxybenzaldehyde (12.2 g, 0.1 mol) was used instead of 3, 4-dihydroxybenzaldehyde (13.8 g, 0.1 mol). (Mw: 2,120)
[ chemical formula A ]
Synthesis comparative example 2
A polymer comprising a structural unit (repeating unit) represented by chemical formula B was synthesized according to the same method as in synthesis example 1, except that pyrene (20.2 g, 0.1 mol) was used instead of 1-hydroxypyrene (21.8 g, 0.1 mol) and 4-hydroxybenzaldehyde (12.2 g, 0.1 mol) was used instead of 3, 4-dihydroxybenzaldehyde (13.8 g, 0.1 mol). (Mw: 2,490)
[ chemical formula B ]
Synthesis comparative example 3
A polymer comprising a structural unit (repeating unit) represented by chemical formula C was synthesized according to the same method as in synthesis example 1, except that pyrene (20.2 g, 0.1 mol) was used instead of 1-hydroxypyrene (21.8 g, 0.1 mol) and benzaldehyde (10.6 g, 0.1 mol) was used instead of 3, 4-dihydroxybenzaldehyde (13.8 g, 0.1 mol). (Mw: 2,008)
[ chemical formula C ]
Synthesis comparative example 4
A polymer comprising a structural unit (repeating unit) represented by chemical formula D was synthesized in the same manner as in synthesis example 1, except that 1-naphthol (14.4 g, 0.1 mol) was used instead of 1-hydroxypyrene (21.8 g, 0.1 mol) and benzaldehyde (10.6 g, 0.1 mol) was used instead of 3, 4-dihydroxybenzaldehyde (13.8 g, 0.1 mol). (Mw: 2,011)
[ chemical formula D ]
Synthesis of comparative example 5
A polymer containing a structural unit (repeating unit) represented by formula E was synthesized in the same manner as in synthesis example 1, except that 4,4' - (9H-fluorene-9, 9-diyl) diphenol (35.0 g, 0.1 mol) was used in place of 1-hydroxypyrene (21.8 g, 0.1 mol). (Mw: 2,472)
[ chemical formula E ]
Evaluation 1 solubility evaluation
5.0 g of the polymers according to synthesis examples 1 to 4 and synthesis comparative examples 1 to 5 were weighed, respectively, uniformly dissolved in 45 g of PGMEA to prepare a 10 wt% solution, and then, filtered with a 0.1 μm TEFLON (tetrafluoroethylene) filter. The filtered samples were each subdivided and weighed using Al dishes whose masses are known to measure the initial mass of the solution. Subsequently, the solvents in the Al dishes were dried in an oven at 160 ℃ for 20 minutes, respectively, and the mass was measured again.
Each solid content of the solution was calculated according to calculation equation 1 from the mass difference before and after drying.
[ calculation equation 1]
Solid content (%) × 100 (mass after drying at 160 ℃ for 20 minutes/initial mass of solution) × 100
(Table 1)
Solubility in PGMEA
Synthesis example 1
O
Synthesis example 2
O
Synthesis example 3
O
Synthesis example 4
O
Synthesis of comparative example 1
△
Synthesis comparative example 2
X
Synthesis comparative example 3
X
Synthesis comparative example 4
O
Synthesis of comparative example 5
O
O: the solid content is more than or equal to 9%
And (delta): the solid content is more than or equal to 8 percent and less than 9 percent
X: the solid content is less than 8 percent
Referring to table 1, the polymers according to synthesis examples 1 to 4 exhibited improved or equal solubility compared to the polymers according to synthesis comparative examples 1 to 5.
Formation of hardmask composition
1.2 grams of the polymers according to synthesis examples 1 to 4 and synthesis comparative examples 1 to 5, respectively, were taken and then uniformly dissolved in 18 grams of PGMEA and filtered with 0.1 micron TEFLON (tetrafluoroethylene) to prepare hardmask compositions according to examples 1 to 4 and comparative examples 1 to 5.
Evaluation 2: evaluation of etching resistance
The hard mask compositions according to examples 1 to 4 and comparative examples 1 to 5 were respectively coated on silicon wafers, and heat-treated on a hot plate at about 400 ℃ for 2 minutes to form organic films.
The thickness of the organic film was measured by using an ST5000 thin film thickness meter manufactured by K-MAC, and then, after that, by using N2/O2Mixed gas (50 mT/300W/10O)2/50N2) After dry etching was performed for one minute, the thickness of the organic film was measured again.
The difference in the thickness of the organic film before and after the dry etching and the etching time is used to calculate a Bulk Etch Rate (BER) according to calculation equation 2.
[ calculation equation 2]
Etch rate (a/s) — (thickness of initial organic film-thickness of organic film after etching)/etch time
The results are shown in table 2.
(Table 2)
Bulk etch rate (angstroms/second)
Example 1
22.21
Example 2
22.35
Example 3
21.67
Example 4
22.72
Comparative example 1
23.05
Comparative example 2
24.25
Comparative example 3
27.60
Comparative example 4
28.53
Comparative example 5
27.21
Referring to table 2, the organic films formed according to the hardmask compositions of examples 1 to 4 exhibited sufficient etch resistance against an etching gas and thus improved etch resistance, as compared to the organic films formed according to the hardmask compositions of comparative examples 1 to 5.
Evaluation 3. film Density
The hard mask compositions according to examples 1 to 4 and comparative examples 1 to 5 were respectively spin-coated on silicon wafers, and then heat-treated on a hot plate at about 400 ℃ for about 2 minutes to form about 1,000 angstrom thick organic films.
The film density of the organic film was measured by an X-ray diffraction apparatus (Malvern PANalytical Ltd).
The results are shown in table 3.
(Table 3)
Film Density (g/cc)
Example 1
1.44
Example 2
1.43
Example 3
1.45
Example 4
1.42
Comparative example 1
1.38
Comparative example 2
1.36
Comparative example 3
1.33
Comparative example 4
1.32
Comparative example 5
1.28
Referring to table 3, the organic films formed according to the hardmask compositions of examples 1 to 4 exhibited improved film densities compared to the organic films formed according to the hardmask compositions of comparative examples 1 to 5.
While the invention has been described in connection with what is presently considered to be practical example embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
- 上一篇：一种医用注射器针头装配设备
- 下一篇：温度控制装置