Polymer, organic layer composition and method of forming pattern
阅读说明：本技术 聚合物、有机层组合物以及形成图案的方法 (Polymer, organic layer composition and method of forming pattern ) 是由 辛乘旭 金昇炫 朴裕信 于 2019-08-20 设计创作，主要内容包括：本发明公开一种包含由化学式1或化学式2表示的结构单元的聚合物、包括所述聚合物的有机层组合物以及使用所述有机层组合物来形成图案的方法。化学式1和化学式2的定义与说明书中所描述的定义相同。<Image he="651" wi="700" file="DDA0002172698260000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(Disclosed are a polymer including a structural unit represented by chemical formula 1 or chemical formula 2, an organic layer composition including the polymer, and a method of forming a pattern using the organic layer composition. The definitions of chemical formula 1 and chemical formula 2 are the same as those described in the specification.)
1. A polymer comprising a structural unit represented by chemical formula 1 or chemical formula 2:
wherein, in chemical formula 1 and chemical formula 2,
b is a substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclyl, or a combination thereof,
a is a single bond, substituted or unsubstituted C1 to C20 alkylene, substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted C2 to C30 heteroarylene, or a combination thereof,
l is a single bond, O, S, NRaCarbonyl, substituted or unsubstituted C1 to C20 alkylene, substituted or unsubstituted C2 to C20 alkenylene, substituted or unsubstituted C2 to C20 alkynylene, substituted or unsubstituted C6 to C30 arylene, or combinations thereof,
Raand R1Each independently a hydrogen atom, a hydroxyl group, a halogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,
p and q are each independently one of an integer from 0 to 4,
r is one of integers of 1 to 5, and
*are the bonding points.
2. The polymer of claim 1, wherein B is represented by any one of the substituents of group I:
[ group I ]
Wherein, in group I,
Ar1is a substituted or unsubstituted C6 to C30 non-fused aryl group,
Ar2is a substituted or unsubstituted four-membered ring (tetragonal ring), a substituted or unsubstituted five-membered ring (pentagonal ring), a substituted or unsubstituted six-membered ring (hexagonal ring) or a fused ring thereof,
x is N, NRbThe oxygen, the oxygen or the sulfur is selected from the group consisting of O and S,
Z1to Z6Each independently is N, C or CRc，
Rb、RcAnd R2To R18Each independently is hydrogen atom, hydroxyl, halogen atom, nitroA carboxyl group, a substituted or unsubstituted imino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof, and
*are the bonding points.
3. The polymer of claim 2, wherein B is represented by one of the substituents of group I-1:
[ group I-1]
Wherein, in group I-1,
Ar3is a C1 to C10 alkyl group or a C6 to C18 aryl group, and
*are the bonding points.
4. The polymer of claim 1, wherein R1And at least one of B is substituted with a hydroxyl group.
5. The polymer of claim 1, wherein B is a substituted or unsubstituted C6 to C30 non-fused aryl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted quinolyl, or a substituted or unsubstituted indolyl.
6. The polymer of claim 5, wherein the substituted or unsubstituted C6 to C30 non-fused aryl is a substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted quaterphenyl, or substituted or unsubstituted pentabiphenyl group.
7. The polymer of claim 1, wherein the structural unit is one of group II:
[ group II ]
Wherein, in group II, is a bonding point.
8. The polymer of claim 1, wherein the weight average molecular weight is from 1,000 to 200,000.
9. An organic layer composition comprising
The polymer of any one of claims 1 to 8, and
a solvent.
10. A method of forming a pattern comprising
A layer of material is disposed on a substrate,
coating the organic layer composition as claimed in claim 9 on the material layer,
heat-treating the organic layer composition to form a hard mask 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
Etching the exposed portions of the material layer.
Technical Field
Disclosed are a polymer, an organic layer composition including the same, and a method of forming a pattern using the organic layer composition.
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 basically require an efficient photolithography technique.
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 organic layer called a hard mask layer may be formed between the material layer and the photoresist layer to provide a fine pattern.
The hard mask layer functions as an intermediate layer for transferring a fine pattern of photoresist to the material layer by a selective etching process. Therefore, the hard mask layer is required to have characteristics such as heat resistance and etching resistance to have resistance during a plurality of etching processes.
Disclosure of Invention
One embodiment provides a polymer that can be effectively applied to a hard mask layer.
Another embodiment provides an organic layer composition comprising the polymer.
Another embodiment provides a method of forming a pattern using the organic layer composition.
According to an embodiment, a polymer includes a structural unit represented by chemical formula 1 or chemical formula 2.
In chemical formula 1 and chemical formula 2,
b is a substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclyl, or a combination thereof,
a is a single bond, substituted or unsubstituted C1 to C20 alkylene, substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted C2 to C30 heteroarylene, or a combination thereof,
l is a single bond, O, S, NRaCarbonyl, substituted or unsubstituted C1 to C20 alkylene, substituted or unsubstituted C2 to C20 alkenylene, substituted or unsubstituted C2 to C20 alkynylene, substituted or unsubstituted C6 to C30 arylene, or combinations thereof,
Raand R1Each independently a hydrogen atom, a hydroxyl group, a halogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,
p and q are each independently one of an integer from 0 to 4,
r is one of integers of 1 to 5, and
*are the bonding points.
B may be represented by any one of the substituents of group I.
[ group I ]
In the group I, the group I is,
Ar1is a substituted or unsubstituted C6 to C30 non-fused aryl group,
Ar2is a substituted or unsubstituted four-membered ring (tetragonal ring), a substituted or unsubstituted five-membered ring (pentagonal ring), a substituted or unsubstituted six-membered ring (hexagonal ring) or a fused ring thereof,
x is N, NRbThe oxygen, the oxygen or the sulfur is selected from the group consisting of O and S,
Z1to Z6Each independently is N, C or CRc，
Rb、RcAnd R2To R18Each independently is a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, a substituted or unsubstituted imino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof, and
*are the bonding points.
B may be represented by one of the substituents of group I-1.
[ group I-1]
In the group I-1, the group,
Ar3is a C1 to C10 alkyl group or a C6 to C18 aryl group, and
*are the bonding points.
For example, R of chemical formulas 1 and 21At least one of B and B may be substituted with a hydroxyl group.
B may be a substituted or unsubstituted C6 to C30 non-fused aryl, substituted or unsubstituted naphthyl, substituted or unsubstituted quinolyl, or substituted or unsubstituted indolyl.
The substituted or unsubstituted C6-C30 non-fused aryl group may be a substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, or substituted or unsubstituted pentabiphenyl group.
The structural unit may be one of group II.
[ group II ]
In the group II, the first group of the compounds,*are the bonding points.
The weight average molecular weight of the polymer may range from about 1,000 to about 200,000.
According to another embodiment, there is provided an organic layer composition comprising the aforementioned polymer and a solvent.
The polymer may be included in an amount of about 0.1 wt% to about 50 wt% based on the total amount of the organic layer composition.
According to another embodiment, a method of forming a pattern includes: providing a material layer on a substrate; coating an organic layer composition on the material layer; heat-treating the organic layer 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 portions of the material layer.
When the polymer according to an embodiment is used as the organic layer material, an organic layer having improved etching resistance may be provided.
Detailed Description
Exemplary embodiments of the present invention will be described in detail below, 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 exemplary embodiments set forth herein.
As used herein, "substituted," when a definition is not otherwise provided, may refer to replacement of a hydrogen atom of a compound by a substituent selected from the group consisting of: halogen atoms (F, Br, Cl, or I), hydroxyl groups, nitro groups, cyano groups, amino groups, azido groups, amidino groups, hydrazine groups, hydrazono groups, carbonyl groups, carbamoyl groups (carbamyl groups), thiol groups, ester groups, carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, C1 to C30 alkyl groups, C2 to C30 alkenyl groups, C2 to C30 alkynyl groups, C6 to C30 aryl groups, C7 to C30 aralkyl groups, C1 to C30 alkoxy groups, C1 to C20 heteroalkyl groups, C3 to C20 heteroaralkyl groups, C3 to C30 cycloalkyl groups, C3 to C15 cycloalkenyl groups, C6 to C15 cycloalkynyl groups, C2 to C30 heteroaryl groups, and combinations thereof.
As used herein, when a definition is not otherwise provided, the term "hetero" refers to a group comprising 1 to 3 heteroatoms selected from N, O, S and P.
As used herein, "aryl" may refer to a group comprising at least one hydrocarbon aromatic moiety, and includes a hydrocarbon aromatic moiety linked by a single bond and a hydrocarbon aromatic moiety fused directly or indirectly to provide a non-aromatic fused ring. 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 in place of carbon (C) in a cyclic compound (e.g., aryl, cycloalkyl, fused rings thereof, or combinations thereof). When the heterocyclyl group is a fused ring, all or each ring of the heterocyclyl group may contain one or more heteroatoms.
More specifically, the substituted or unsubstituted aryl group and/or the substituted or unsubstituted heterocyclic group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted tetracenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl groupA phenyl group (chrysenyl group), a substituted or unsubstituted triphenylene group (triphenylenyl group), a substituted or unsubstituted perylene group (perylenyl group), a substituted or unsubstituted indenyl group (indenylenyl group), a substituted or unsubstituted furyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, Substituted or unsubstituted benzothienyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiaAn azole group, a substituted or unsubstituted acridine group (acridine group), a substituted or unsubstituted phenazine group, a substituted or unsubstituted phenothiazine group, a substituted or unsubstituted phenoxazine group, a substituted or unsubstituted fluorenyl (fluornyl group), a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, pyridoindolyl group, benzopyridyl oxazinyl group, benzopyridyl thiazinyl group, 9-dimethyl-9,10-dihydroacridinyl (9,9-dimethyl-9,10-dihydroacridinyl group), combinations thereof or rings fused with combinations of the foregoing groups, but is not limited thereto. In one embodiment of the invention, the heterocyclyl or heteroaryl group can be imidazolyl, thienyl, pyridyl, pyrimidinyl, or indolyl.
As used herein, a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group may be a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclyl group having two linking groups as described previously, such as a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted quaterphenylene group, a substituted or unsubstituted heteroarylene groupA group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted peryleneene group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanylene group, a substituted or unsubstituted thiophenylene group, a substituted or unsubstituted pyrrolylene group, a substituted or unsubstituted pyrazolylene group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolylene group, a substituted or unsubstituted oxazolylene group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxa groupA diazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridinylene group, a substituted or unsubstituted pyrimidinylene group, a substituted or unsubstituted pyrazinylene group, a substituted or unsubstituted benzothienylene group, a substituted or unsubstituted benzofuranylene group, a substituted or unsubstituted benzothiophene group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolylene group, a substituted or unsubstituted isoquinolylene group, a substituted or unsubstituted quinazolinylene group, a substituted or unsubstituted quinoxalylene group, a substituted or unsubstituted naphthyrylene group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzothiazolyl group, a substituted or unsubstituted acridinylene group, Substituted or unsubstituted phenazinylene, substituted or unsubstituted phenothiazinylene, substituted or unsubstituted phenoxazylene, substituted or unsubstituted fluorenylene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenylene, substituted or unsubstituted carbazolyl, combinations thereof or fused rings of combinations of the foregoing, but are not limited thereto.
As used herein, "non-fused aryl" refers to at least one monocyclic aryl group that is linked to a sigma-bond.
More specifically, "non-fused aryl" refers to a phenyl group bonded to a sigma-bond, and in one example of the present invention, "non-fused aryl" may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, or the like, but is not limited thereto.
Hereinafter, the polymer according to the example is described.
A polymer according to an embodiment includes a structural unit represented by chemical formula 1 or chemical formula 2.
In chemical formula 1 and chemical formula 2,
b is a substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C30 heterocyclyl, or a combination thereof,
a is a single bond, substituted or unsubstituted C1 to C20 alkylene, substituted or unsubstituted C6 to C30 arylene, substituted or unsubstituted C2 to C30 heteroarylene, or a combination thereof,
l is a single bond, O, S, NRaCarbonyl, substituted or unsubstituted C1 to C20 alkylene, substituted or unsubstituted C2 to C20 alkenylene, substituted or unsubstituted C2 to C20 alkynylene, substituted or unsubstituted C6 to C30 arylene, or combinations thereof,
Raand R1Each independently a hydrogen atom, a hydroxyl group, a halogen atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,
p and q are each independently one of an integer from 0 to 4,
r is one of integers of 1 to 5, and
and is a bond site.
Since the polymer contains the structural units in a staggered configuration (including a vinyl main chain), even with a high carbon content, the solubility to a solvent is high enough to be effectively applied in a solution process such as spin coating, and the etching resistance is also high enough to withstand an etching gas exposed in a subsequent etching process.
In particular, the polymer may increase solubility to an organic solvent due to structural characteristics of a structural unit included in the polymer even though a hydrophilic functional group such as a hydroxyl group (-OH) is not introduced, and thus affinity to an underlying film is increased, so that the obtained hard mask layer may have improved film flatness.
For example, B may be represented by one of group I.
[ group I ]
In the group I, the group I is,
Ar1is a substituted or unsubstituted C6 to C30 non-fused aryl group,
Ar2is a substituted or unsubstituted four-membered ring, a substituted or unsubstituted five-membered ring, a substituted or unsubstituted six-membered ring or a condensed ring thereof,
x is N, NRbThe oxygen, the oxygen or the sulfur is selected from the group consisting of O and S,
Z1to Z6Each independently is N, C or CRc，
Rb、RcAnd R2To R18Each independently is a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, a substituted or unsubstituted imino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof, and
*are the bonding points.
For example, B may be represented by one of the substituents of group I-1.
[ group I-1]
In the group I-1, the group,
Ar3is a C1 to C10 alkyl group or a C6 to C18 aryl group,
*are the bonding points.
For example, R of chemical formulas 1 and 21At least one of B and B may be substituted with a hydroxyl group.
When a hydrophilic functional group such as a hydroxyl group is introduced, the degree of crosslinking can be increased, and the flatness can be further increased depending on the type of substrate.
For example, B may be a substituted or unsubstituted C6 to C30 non-fused aryl, substituted or unsubstituted naphthyl, substituted or unsubstituted quinolyl, or substituted or unsubstituted indolyl.
The substituted or unsubstituted C6-C30 non-fused aryl group may be a substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, or substituted or unsubstituted pentabiphenyl group.
The structural unit according to the exemplary embodiment of the present invention may be one of group II, but is not limited thereto.
[ group II ]
In the group II, the first group of the compounds,*are the bonding points.
Meanwhile, when the polymer is applied to a process including UV exposure, an intermolecular crosslinking reaction may be induced by a mechanism of a cycloaddition between vinyl backbones.
Thus, the polymer can exhibit photosensitive characteristics without a photosensitive additive, and can control etching resistance and film thickness shrinkage by exposure dose difference in each region of the film using photosensitive characteristics, and can provide a patterning function by itself even without a subsequent photolithography process.
The polymer may have a weight average molecular weight of about 1,000 to about 200,000. When the polymer has a weight average molecular weight within the range, it is possible to optimize the carbon content and solubility to a solvent of an organic layer composition including the polymer (e.g., a hardmask composition).
According to another embodiment, there is provided an organic layer composition comprising the aforementioned polymer and a solvent.
The solvent may be any one having sufficient solubility or dispersibility with respect to the polymer, and may include, for example, at least one selected from the group consisting of: propylene glycol, propylene glycol diacetate, methoxypropylene glycol, diethylene glycol butyl ether, tris (ethylene glycol) monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N-dimethylformamide, N-dimethylacetamide, methylpyrrolidone, acetylacetone, ethyl 3-ethoxypropionate, 4-methoxybenzene and tetrahydronaphthalene (tetrahydronaphthalene).
The polymer may be included in an amount of about 0.1 wt% to about 50 wt%, for example in an amount of about 0.5 wt% to about 40 wt%, about 1 wt% to about 30 wt%, or about 5 wt% to about 20 wt%, based on the total amount of the organic layer composition. When the polymer is included in the range, the thickness, surface roughness, and planarization of the organic layer can be controlled.
The organic layer composition may further comprise additives of surfactants, cross-linking agents, thermal acid generators, or plasticizers.
The surfactant may include, for example, fluoroalkyl-based compounds (fluorinated compounds), alkyl benzene sulfonate(s), alkyl pyridinium salts, polyethylene glycol(s), or quaternary ammonium salts(s), 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 crosslinking-forming substituents, such as a compound such as methoxymethylated glycoluril (methoxymethylated glycoluril), butoxymethylated glycoluril (butoxymethylated glycoluril), methoxymethylated melamine (methoxymethylated melamine), butoxymethylated benzoguanamine (methoxymethylated benzoguanamine), butoxymethylated benzoguanamine (butoxymethylated benzoguanamine), methoxymethylated urea (methoxymethylated urea), butoxymethylated urea (butoxymethylated urea), methoxymethylated thiourea (methoxymethylated thiourea), or butoxymethylated thiourea (methoxymethylated thiourea), etc.
The crosslinking agent may be a crosslinking agent having higher heat resistance. The crosslinking agent having higher heat resistance may be a compound containing a crosslinking substituent having 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-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid (hydroxybenzoic acid), naphthalene carbonic acid, etc., or/and 2,4,4,6-tetrabromocyclohexadienone (2,4,4,6-tetrabromocyclohexadienone), benzoin tosylate, 2-nitrobenzyl tosylate (2-nitrobenzyl tosylate), other organic alkyl sulfonates, etc., but is not limited thereto.
The additive may be included in an amount of about 0.001 parts by weight to about 40 parts by weight, based on 100 parts by weight of the organic layer composition. Within the range, the solubility may be improved without changing the optical properties of the organic layer composition.
According to another embodiment, there is provided an organic layer manufactured using the aforementioned organic layer composition. The organic layer may be formed, for example, by coating the aforementioned organic layer composition on a substrate and heat-treating it for curing, and may include, for example, a hard mask layer for an electronic device, a planarization layer, a sacrificial layer, a filler, and the like.
Hereinafter, a method of forming a pattern using the aforementioned organic layer composition is described.
The method of forming a pattern according to an embodiment includes: providing a material layer on a substrate; coating an organic layer composition including a polymer and a solvent on the material layer; heat-treating the organic layer 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 portions 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 organic layer composition is the same as described above and can be applied in solution by spin coating. Herein, the thickness of the organic layer composition is not particularly limited, but may be, for example, about 50 angstroms to about 200,000 angstroms.
The organic layer composition may be heat treated at, for example, about 100 c to about 700 c for about 10 seconds to about 1 hour.
For example, the method may further comprise 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/or the like.
For example, the method may further comprise: before forming the photoresist layer, a bottom anti-reflective coating (BARC) layer is formed on an upper surface of the silicon-containing thin layer or on an upper surface of the hard mask layer.
The photoresist layer may be exposed using, for example, ArF, KrF, or EUV. After exposure, a heat 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, 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, etc., such as different patterns of a semiconductor integrated circuit device.
Hereinafter, the present disclosure is explained in more detail with reference to examples. However, these examples are exemplary, and the present disclosure is not limited thereto.
Synthesis examples
Synthesis example 1
After a distillation apparatus was installed in the flask, 5 g of 4-ethynylbiphenyl (ethylbiphenylyl) and 1g of azobisisobutyronitrile (hereinafter, referred to as AIBN) as a catalyst were added thereto, and then 18 g of dichlorobenzene was added and dissolved by stirring it. It was reacted by heating at 100 ℃ for 24 hours and then cooled to 20 ℃. 10 grams of tetrahydrofuran was added to the reaction solution to dilute the solution, and the diluted solution was poured into 1 liter of n-hexane/isopropanol mixed solution (7/3). The precipitated compound was filtered and washed with n-hexane, and vacuum-dried to provide a polymer comprising the structural unit represented by chemical formula 1 a.
The weight average molecular weight (Mw) of the polymer measured by Gel Permeation Chromatography (GPC) was 1,500.
[ chemical formula 1a ]
Synthesis example 2
A polymer comprising a structural unit represented by chemical formula 1b was prepared according to the same procedure as in synthesis example 1, except that 5.5 g of 4-ethynyl- [1,1'-biphenyl ] -4-ol (4-ethynyl- [1,1' -biphenyl ] -4-ol) was used instead of 5 g of 4-ethynyl biphenyl in synthesis example 1.
Weight average molecular weight was 2,000 as measured using Gel Permeation Chromatography (GPC).
[ chemical formula 1b ]
Synthesis example 3
A polymer comprising a structural unit represented by chemical formula 1c was prepared according to the same procedure as in synthesis example 1, except that 4.3 g of 2-ethynyl-naphthalene (2-ethynyl-naphthalene) was used instead of 5 g of 4-ethynyl biphenyl in synthesis example 1.
The weight average molecular weight of the polymer was 1,300 as measured using gel permeation chromatography.
[ chemical formula 1c ]
Synthesis example 4
A polymer comprising a structural unit represented by chemical formula 1d was prepared according to the same procedure as in synthesis example 1, except that 5.5 g of 1-ethynyl-4-phenoxybenzene (1-ethyl-4-phenoxybenzene) was used instead of 5 g of 4-ethynylbiphenyl in synthesis example 1.
The weight average molecular weight of the polymer was 1,500 as measured using gel permeation chromatography.
[ chemical formula 1d ]
Synthesis example 5
A polymer comprising a structural unit represented by chemical formula 1e was prepared according to the same procedure as in synthesis example 1, except that 6.3 g of 4'- (2-propyn-1-yloxy) [1,1' -biphenyl ] -4-ol (4 '(2-propyln-1-yloxy) [1,1' -biphenyl ] -4-ol) was used instead of 5 g of 4-ethynylbiphenyl in synthesis example 1.
The weight average molecular weight of the polymer was 1,500 as measured using gel permeation chromatography.
[ chemical formula 1e ]
Synthesis example 6
A polymer comprising a structural unit represented by chemical formula 1f was prepared according to the same procedure as in synthesis example 1, except that 6.9 g of 3- (2-ethynyl-6-quinolinyl) -phenol (3- (2-ethyl-6-quinolinyl) -phenol) was used instead of 5 g of 4-ethynylbiphenyl in synthesis example 1.
The weight average molecular weight of the polymer was 1,500 as measured using gel permeation chromatography.
[ chemical formula 1f ]
Synthesis example 7
A polymer comprising a structural unit represented by chemical formula 1g was prepared according to the same procedure as in synthesis example 1, except that 5.7 g of 1-ethynyl-4- (2-phenylvinyl) benzene was used instead of 5 g of 4-ethynyl biphenyl in synthesis example 1.
The weight average molecular weight of the polymer was 1,500 as measured using gel permeation chromatography.
[ chemical formula 1g ]
Synthesis example 8
After a distillation apparatus was installed in a flask filled with nitrogen gas, 5 g of 2-methyl 4- (naphthalen-2-yl) but-3-yn-2-ol (manufactured by reike Metals NCS Brand) and 0.5 g of catalyst tungsten hexachloride (WCl)6) And then 18 grams of dichlorobenzene was added and dissolved by stirring it. It was reacted by heating at 40 ℃ for 6 hours and then cooled to 20 ℃. 10 g of tetrahydrofuran was added to the reaction solution to dilute the solution, and the diluted solution was added to 2L of methanol to produce a precipitate. The precipitated compound was filtered and washed with n-hexane, and vacuum-dried to provide a polymer comprising the structural unit represented by chemical formula 1 h. The polymer was confirmed to have a weight average molecular weight of 3,000 by GPC.
[ chemical formula 1h ]
Comparative Synthesis example 1
A polymer comprising a structural unit represented by the chemical formula Y1 was prepared according to the same procedure as in synthesis example 1, except that 5.5 g of hydroxystyrene (hydroxystyrene) was used instead of 5 g of 4-ethynylbiphenyl in synthesis example 1.
The weight average molecular weight of the polymer was 3,800 as measured using gel permeation chromatography.
[ chemical formula Y1]
Comparative Synthesis example 2
A polymer comprising a structural unit represented by the chemical formula Y2 was prepared according to the same procedure as in synthesis example 1, except that 7 g of 4-vinylbiphenyl was used instead of 5.5 g of hydroxystyrene in comparative synthesis example 1.
The weight average molecular weight of the polymer was measured using gel permeation chromatography to be 4,500.
[ chemical formula Y2]
Forming an organic layer
Each of the polymers obtained from synthesis examples 1 to 8 and comparative synthesis examples 1 to 2 was weighed 1g and dissolved in 10 g of Propylene Glycol Monomethyl Ether Acetate (PGMEA), and stirred for 24 hours and then filtered through 0.1 micrometer filter paper to provide a hardmask composition. The composition was coated on a silicon wafer according to a spin coating method and heated at 350 ℃ for 2 minutes under an air atmosphere to provide a thin film.
Evaluation of
Evaluation 1: resistance to etching
The thicknesses of the organic layers according to examples 1 to 8 and comparative examples 1 to 2 were measured. Subsequently, using CFx/Ar/O2The mixed gases were used to dry etch the organic layer for 50 seconds and then the thickness of the organic layer was measured again.
Using the thicknesses of the organic layers before and after the dry etching and the etching times corresponding thereto, the Bulk Etch Rate (BER) was calculated according to calculation equation 1, and evaluation grades were individually given with reference to the criteria defined in table 2 and shown in table 1.
[ calculation equation 1]
Etch rate (a/s) — (initial organic layer thickness-organic layer thickness after etching)/etch time
[ Table 1]
Rating of evaluation
Example 1
B
Example 2
B
Example 3
A
Example 4
B
Example 5
B
Example 6
A
Example 7
A
Example 8
A
Comparative example 1
C
Comparative example 2
C
[ Table 2]
Grade
Evaluation criteria for etch Rate/etch resistance
A
Etch rate<25 angstroms/second
B
Etching rate is more than or equal to 25 angstroms/second and less than or equal to 30 angstroms/second
C
Etch rate>30 angstroms/second
Referring to tables 1 and 2, it can be confirmed that the thin films obtained from the hard mask compositions according to examples 1 to 8 exhibit improved bulk etching characteristics so as to provide sufficient etching resistance against etching gas, as compared to the thin films obtained from the hard mask compositions according to comparative examples 1 and 2.
While the invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not to be limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.