WO2018021619A1 - Organic film composition and pattern formation method - Google Patents
Organic film composition and pattern formation method Download PDFInfo
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- WO2018021619A1 WO2018021619A1 PCT/KR2016/011703 KR2016011703W WO2018021619A1 WO 2018021619 A1 WO2018021619 A1 WO 2018021619A1 KR 2016011703 W KR2016011703 W KR 2016011703W WO 2018021619 A1 WO2018021619 A1 WO 2018021619A1
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- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000007261 regionalization Effects 0.000 title claims abstract 3
- 229920000642 polymer Polymers 0.000 claims abstract description 82
- 239000000126 substance Substances 0.000 claims abstract description 54
- 125000003118 aryl group Chemical group 0.000 claims abstract description 46
- 239000000654 additive Substances 0.000 claims abstract description 45
- 230000000996 additive effect Effects 0.000 claims abstract description 41
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 25
- 125000003277 amino group Chemical group 0.000 claims abstract description 16
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 15
- 125000002560 nitrile group Chemical group 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 9
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- 239000010408 film Substances 0.000 claims description 61
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 36
- 125000005843 halogen group Chemical group 0.000 claims description 29
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- 150000002367 halogens Chemical class 0.000 claims description 28
- 239000010409 thin film Substances 0.000 claims description 28
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
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- 125000001072 heteroaryl group Chemical group 0.000 claims description 18
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- 229910052710 silicon Inorganic materials 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
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- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 7
- 125000000962 organic group Chemical group 0.000 claims description 7
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 33
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- 239000002244 precipitate Substances 0.000 description 3
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- 150000003672 ureas Chemical class 0.000 description 3
- DAJPMKAQEUGECW-UHFFFAOYSA-N 1,4-bis(methoxymethyl)benzene Chemical compound COCC1=CC=C(COC)C=C1 DAJPMKAQEUGECW-UHFFFAOYSA-N 0.000 description 2
- MVKDNXIKAWKCCS-UHFFFAOYSA-N 3-methyl-1h-pyridin-2-one Chemical compound CC1=CC=CN=C1O MVKDNXIKAWKCCS-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 2
- CPXIBWAVNCSOPW-UHFFFAOYSA-N 5-hydroxynaphthalene-1-carbaldehyde Chemical compound C1=CC=C2C(O)=CC=CC2=C1C=O CPXIBWAVNCSOPW-UHFFFAOYSA-N 0.000 description 2
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical class NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 2
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- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
- H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
Definitions
- a hard mask layer (hard mask layer) may be formed.
- the hard mask layer serves as an interlayer that transfers the fine pattern of the photoresist to the material layer through a selective etching process. Therefore, the hard mask layer needs properties such as heat resistance and etching resistance to withstand multiple etching processes.
- the hard mask layer is formed by a spin-on coating method instead of a chemical vapor deposition method.
- the spin-on coating method is not only easy to process but can also improve gap-fill and planarization properties.
- heat resistance and etching resistance are in conflict with spin-on characteristics, and an organic film material capable of satisfying both of these properties is required.
- One embodiment provides an organic film composition which can be coated in a spin-on manner and excellent in etching resistance.
- Another embodiment provides a pattern forming method using the organic film composition.
- a polymer comprising a structural unit represented by the following formula (1), an aromatic ring-containing compound substituted or unsubstituted amine group in its structure, It provides an organic film composition comprising an additive comprising at least one substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, or a nitrile group, and a solvent.
- A is a substituted or unsubstituted aromatic ring containing group, a substituted or unsubstituted hetero aromatic ring containing group, or a combination thereof,
- B is a divalent organic group
- At least one of A and B is substituted by a functional group comprising a moiety represented by the following formula (2):
- Z is hydrogen, a hydroxy group, a substituted or unsubstituted C 1 to C 10 alkyl group, or a substituted or unsubstituted C 6 to C 30 atom group,
- the functional group including the moiety represented by Formula 2 may be represented by the following Formula 2 '. [Formula 2 ']
- W is 0, S, NR a or CR b R c , wherein R a to R c are each independently a hydrogen substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group or a combination thereof,
- Z is hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
- a 0 or 1
- b is an integer from 0 to 10
- the additive may be represented by the following formula (3).
- X is a direct bond,-(C q H 2q )-,-(C t R w 2t )-, oxygen (0), sulfur (S), -NH-, or -S (0 2 )-, wherein q and t are each independently an integer of 1 to 5 and R w is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, Substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C 1 to C20 alkylamine group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted C 1 to C20 heteroalkyl group, substituted or Unsubstituted C2 to C30
- Heterocycloalkyl group substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C 1 to C4 alkyl ether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C 1 To C30 haloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,
- the additive may be represented by the following formula (4) or (5).
- X 1 is -CH- or nitrogen (N),
- X 2 is a direct bond,-(C q H 2q )-,-(C t R w 2t )-, oxygen (0), sulfur (S), -NH- or -S (0 2 )-, wherein q And t are each independently an integer of 1 to 5 and R w is a substituted or unsubstituted C 1 to C20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 3 to C 30 cycloalkenyl group, substituted Or an unsubstituted C 1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C 1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30
- Heterocycloalkyl group substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C1 to C4 alkyl ether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C 1 to C30 haloalkyl group, substituted or Unsubstituted C2 to C20 alkenyl group, or a combination thereof,
- R 1 to R 5 are each independently an aromatic ring-containing group including at least one group represented by the following formula (6):
- W is 0, S, NR a or CR b R c , wherein R a to R c are each independently a hydrogen substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group or a combination thereof,
- Y is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, a nitrile group, or a combination thereof,
- a 0 or 1
- b is an integer from 0 to 10
- R 1 to R 5 may be each independently represented by the following Chemical Formula 7.
- R la to R l3a are each independently hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, or a group represented by Formula 6, wherein R la to R 13a At least one is a group represented by the formula (6),
- T 1 and T 2 are each independently 0, S, NR a or CR b R c , wherein R a to ⁇ are each independently hydrogen, a substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group or Combination of these,
- c and d are each independently an integer of 0 to 5
- A may be a substituted or unsubstituted moiety selected from the following groups 1 and 2.
- Z 1 and Z 2 are each independently NR d , 0, S, Te or Se,
- R d and R e are each independently hydrogen, a hydroxy group, a hydroxy group, a special group, a halogen atom, a halogen-containing group, a substituted or unsubstituted 1 to C30 alkyl group, a substituted or
- A may include at least one substituted or unsubstituted aromatic or heteroaromatic ring.
- B may be represented by any one of Formulas Z1 to Z4.
- e and f are each independently 0 or 1
- g is an integer of 1 to 5
- Y 1 to Y 4 are each independently any one of a substituted or unsubstituted moiety selected from Group 3,
- M, M 'and M are each independently a substituted or unsubstituted C1 to C10 alkylene group, 0, S, S0 2 , CR f R g , NR h , or carbonyl, wherein R f to R h are each Independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen containing group or a combination thereof,
- L 1 is a substituted or unsubstituted C6 to C50 arylene group, a substituted or unsubstituted C1 to C10 alkylene oxide containing group, or a combination thereof,
- r is an integer from 0 to 10
- s is an integer from 0 to 10,
- k is an integer of 0-3.
- the polymer may further include a structural unit represented by the following Chemical Formula 8.
- X 0 is a substituted or unsubstituted aromatic ring containing group, a substituted or unsubstituted hetero aromatic ring containing group, or a combination thereof,
- L 0 is a divalent organic group
- X 0 may be a substituted or unsubstituted moiety selected from Groups 1 and 2 below.
- Z 'and Z 2 are each independently NR d , 0, S, Te or Se,
- R d and R e are each independently hydrogen, hydroxy group, hydroxy group, hydroxy group, halogen atom, halogen containing group, substituted or unsubstituted 1 to C30 alkyl group, substituted or Unsubstituted C6 to C30 aryl groups, or a combination thereof.
- the polymer may contain at least one oxygen atom in its structural unit.
- Formula 2 may be represented by the following formula (2 ').
- W is 0, S, NR a or CR b R c , wherein R a to! Are each independently a hydrogen substituted or unsubstituted C 1 to C 20 alkyl group, a halogen atom, a halogen containing group or a combination thereof,
- a 0 or 1
- the additive may be represented by any one of the following formulas Y1 to Y4. [Formula Yi]
- ⁇ 3 and ⁇ 4 are each independently 0, S, NR a or CR b R c , wherein R a to R c are each independently hydrogen, a substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group Or a combination thereof,
- R x to R y are each independently hydrogen, a halogen atom, a halogen-containing group, or a substituted or unsubstituted C1 to C20 alkyl group,
- R 33 to R 55 are each independently a group represented by the following formula (6):
- W is 0, S, NR a or CR b R c , wherein R a to R c are each independently hydrogen, a substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group or a combination thereof,
- Y is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, a nitrile group, or a combination thereof, a is 0 or 1,
- b is an integer from 0 to 10
- the additive may have a molecular weight of 150 to 50,000.
- the polymer may have a weight average molecular weight of 500 to 200,000.
- the additive may comprise from 5 parts by weight 0 /. To 50% by weight, based on the total amount of the organic film composition.
- Applying the organic film composition may be performed by a spin-on coating method.
- the heat treatment may include a first heat treatment performed at 50 to 250 ° C., and a second heat treatment following the first heat treatment and performed at 200 to 500 ° C.
- the method may further include forming a bottom anti-reflection layer (BARC) before forming the photoresist layer.
- BARC bottom anti-reflection layer
- the predetermined polymer and the predetermined additive By including the predetermined polymer and the predetermined additive, it is possible to provide an organic film composition which can be coated in a spin-on manner and excellent in etching resistance.
- the organic film prepared from the organic film composition is excellent in both film density and film flatness.
- FIG. 1 is a diagram for explaining a method for evaluating flattening characteristics (difference characteristics), and FIG. 2 is a diagram for explaining a method for evaluating thickness uniformity characteristics.
- substituted means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl, or 1), hydroxy group, alkoxy group, nitro group, cyano group, amino group, azido group, amine Dino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thi group, ester group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 To C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C 1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C2 to C20 heteroaryl group, C3 to C20
- a substituent selected from a heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and a combination thereof.
- hetero means containing 1 to 3 heteroatoms selected from N, 0, S and P.
- the organic film composition according to the embodiment is a polymer comprising a structural unit represented by the following formula (1), a substituted or unsubstituted amine group as an aromatic ring-containing compound, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group It provides an organic film composition comprising an additive comprising at least one, an azide group, or a nitrile group, and a solvent.
- A is a substituted or unsubstituted aromatic ring containing group, a substituted or unsubstituted hetero aromatic ring containing group, or a combination thereof,
- B is a divalent organic group, At least one of A and B is substituted by a functional group comprising a moiety represented by the following formula (2):
- Z is hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
- the organic film composition includes a polymer having a predetermined structure and an additive having a predetermined structure. First, the said polymer is demonstrated.
- the polymer comprises a connector portion, and a structural unit containing alone or in combination of two or more, which is represented by the formula 1, represented as B-containing portion and an aromatic group represented by A in the above structural units.
- A may be a substituted or unsubstituted aromatic ring-containing group, and may include, for example, a substituted or unsubstituted moiety selected from Group 1, but is not limited thereto.
- A may be a substituted or unsubstituted heteroaromatic ring-containing group, and may include, for example, a substituted or unsubstituted moiety selected from Group 2, but is not limited thereto.
- ⁇ 1 and ⁇ 2 are each independently NR d , 0, S, Te, or Se,
- Z 3 and Z 4 are N, R d and R e are each independently hydrogen, hydroxy group, methoxy group, ethoxy group, halogen atom, halogen containing group, substituted or unsubstituted 1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, or their It is a combination.
- A may be a combination of a substituted or unsubstituted aromatic ring-containing group, and a substituted or unsubstituted hetero aromatic ring-containing group.
- A may be two or more substituted or It may comprise an unsubstituted benzene ring, for example two to six substituted or unsubstituted benzene rings.
- the benzene ring may be substituted by at least one hydroxy group.
- B representing the linking group in Chemical Formula 1 may be a divalent organic linear group, a divalent organic ring group, or a combination thereof.
- B may be represented by any one of Formulas Z1 to Z4, but is not limited thereto.
- e and f are each independently 0 or 1 g is an integer of 1 to 5,
- Y 1 to Y 4 are each independently any one of a substituted or unsubstituted moiety selected from Group 3,
- M, M 'and M are each independently a substituted or unsubstituted C1 to C10 alkylene group 0, S, S0 2 , CR f R g , NR h , or carbonyl, wherein R f to R h are each independently Hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof,
- L 1 is a substituted or unsubstituted C6 to C50 arylene group, a substituted or unsubstituted C1 to C10 alkylene oxide containing group, or a combination thereof,
- r is an integer from 0 to 10
- s is an integer of 3 to 10
- k is an integer of 1 to 3.
- at least one of A and B is substituted by an acetylene-containing group represented by Formula 2.
- the aromatic ring-containing group or the heteroaromatic ring-containing group represented by A may be substituted by an acetylene-containing group
- the linking group represented by B may be substituted by an acetylene-containing group
- both the A and B portions may be acetylene. It may be substituted by the containing group.
- the number of substitutions is not particularly limited.
- the functional group including the moiety represented by Chemical Formula 2 may be a group represented by Chemical Formula 2 ', but is not limited thereto.
- W is 0, S, NR a or CR b R ⁇ l, wherein R a to! Are each independently a hydrogen substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group, or a combination thereof,
- Z is hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
- a 0 or 1
- b is an integer from 0 to 10
- the functional group including the moiety represented by Formula 2 may be a group represented by Formula 2 ′′, but is not limited thereto. [Formula 2 "]
- W is 0, S, NR a or CR b R c , wherein R a to R c are each independently hydrogen : a substituted or unsubstituted C 1 to C 20 alkyl group, a halogen atom, a halogen containing group or a combination thereof,
- a 0 or 1
- the polymer may include at least one oxygen atom in its structure.
- the polymer can secure etch resistance by including the aromatic ring-containing group or heteroaromatic ring-containing group represented by A in the structural unit, and flexibility by securing the organic group represented by B. have.
- the acetylene forms a ring structure when the polymer is cured, thereby further improving the etching resistance of the polymer. Accordingly, the organic film formed by using the polymer is excellent in film density. In addition, the organic film formed by using the polymer can ensure thickness uniformity.
- the polymer may further include a structural unit represented by the following Chemical Formula 8.
- X 0 is a substituted or unsubstituted aromatic ring containing group, a substituted or unsubstituted hetero aromatic ring containing group, or a combination thereof,
- L 0 is a divalent organic group
- X may be a substituted or unsubstituted moiety selected from Groups 1 and 2, and L 0 is as described for ⁇ of Formula 1 as a linking group.
- the structural unit represented by Chemical Formula 8 does not necessarily include an acetylene functional group.
- the additive includes at least one substituted or unsubstituted amine group, substituted or unsubstituted vinyl group, substituted or unsubstituted acetylene group, azide group, or nitrile group as the aromatic ring-containing compound.
- the additive may be represented by the following formula (3).
- X is a direct bond,-(C q H 2q )-,-(C t R w 2t )-, oxygen (0), sulfur (S), -NH-, or
- ⁇ is a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, substituted or unsubstituted A substituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C 1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or
- Heterocycloalkyl group substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C 1 to C4 alkyl ether group, substituted or unsubstituted C7 to C20 Arylalkylene ether group, substituted or unsubstituted C1 to C30 haloalkyl group, substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,
- R 'and R' ' are each independently a substituted or unsubstituted aromatic ring containing group
- R, R ′, or R ′′ may be, for example, one or two substituted or unsubstituted amine groups, a substituted or unsubstituted vinyl group.
- Substituted or unsubstituted acetylene group, azide group, or nitrile group may be substituted.
- the additive represented by Chemical Formula 3 has a structure in which two or three aromatic ring-containing groups are connected to the core represented by X.
- the core is carbon or nitrogen
- the core is a direct bond, carbon, oxygen, sulfur, or -S (0 2 )-.
- the additive when the additive has a structure in which three aromatic ring-containing groups are connected to the core, it may be represented by the following Formula 4, and when the additive has a structure in which two aromatic ring-containing groups are connected to the core, it is represented by the following Formula 3 Can be.
- X 1 is — CH- or nitrogen (N)
- X 2 is a direct bond,-(C q H 2 q)-,-(C t R w 2t )-, oxygen (0), sulfur (S), -NH- or -S (0 2 )-, wherein q and t are each independently integers of 1 to 5 and ⁇ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or Unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted CI to C20 heteroalkyl group, substituted or unsubstituted C2 to C30
- Heterocycloalkyl group substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C1 to C4 alkyl ether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C1 to C30 Haloalkyl group, substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,
- R 1 to R 5 are each independently an aromatic ring containing group containing at least one group represented by the following formula (6) in its structure:
- W is 0, S, NR a or CR b R c , wherein R a to ⁇ are each independently a hydrogen substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group or a combination thereof,
- Y is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, a nitrile group, or a combination thereof,
- a 0 or 1
- b is an integer from 0 to 10
- R 1 to R 5 may be each independently represented by the following Formula 7, but are not limited thereto. [Formula 7]
- R la to are each independently hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, or a group represented by Formula 6, wherein at least one of R la to R 13a is a group represented by Formula 6,
- T 1 and T 2 are each independently 0, S, NR a or CR b R c , wherein R a to R c are each independently hydrogen, a substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group Or a combination thereof,
- c and d are each independently an integer of 0 to 5
- the additive may be represented by any one of the following Formulas Y1 to Y4, but is not limited thereto.
- ⁇ 3 and ⁇ 4 are each independently 0, S, NR a or CR b R c , wherein R a to R c are each independently hydrogen, a substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing Groups or a combination thereof,
- R x to R y are each independently hydrogen, a halogen atom, a halogen-containing group, or a substituted or unsubstituted C1 to C20 alkyl group,
- R 33 to R 55 are each independently a group represented by Formula 6 above.
- the additive may include at least one oxygen atom or nitrogen atom in the structure thereof, for example, 1 to 3 oxygen atoms. It may include, but is not limited to, an atom or one nitrogen atom.
- the additive can act, for example, as a crosslinking agent.
- the organic film composition may include a polymer having acetylene introduced therein, and an substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, or nitrile as an aromatic ring-containing compound.
- Additives comprising at least one group.
- the carbon content is relatively increased as the acetylene functional group introduced into the polymer reacts with the amine, acetylene, and azide introduced into the additive during curing to form a ring. Accordingly, the etching resistance may be improved, and the etch selectivity may be improved. Therefore, the organic film formed using the organic film composition is excellent in film density and pattern formability.
- the polymer may have a weight average molecular weight of about 500 to 200,000.
- the weight average molecular weight in the above range for the carbon content and the solvent of the organic film composition (eg, hard mask composition) comprising the polymer Solubility can be adjusted to optimize.
- the additive may have a molecular weight of about 150 to 50,000.
- the solvent included in the organic film composition is not particularly limited as long as it has a good solubility or dispersibility in the polymer, for example, propylene glycol, propylene glycol diacetate, mesopropanediol, diethylene glycol,
- Diethylene glycol butyl ether tri (ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclonucleanone, ethyl lactate, gamma-butyrolactone, ⁇ , ⁇ -dimethylformamide, And at least one selected from ⁇ , ⁇ -dimethylacetamide, methylpyridone, methylpyridinone, acetylacetone and ethyl 3-ethoxypropionate.
- the polymer may be included in about 0.1 to 50% by weight based on the total content of the organic film composition. By including the polymer in the above range it is possible to control the thickness, surface roughness and degree of planarization of the organic film.
- the additive may be included in about 0.1 to 50% by weight based on the total content of the organic film composition, for example, may be included in about 5 to 50% by weight 0 /. By including the additive in the above range it is possible to improve the initial planarization of the organic film produced.
- the organic film composition may further include additives such as a surfactant, a crosslinking agent, a thermal acid generator, and a plasticizer.
- additives such as a surfactant, a crosslinking agent, a thermal acid generator, and a plasticizer.
- the surfactant may be, for example, alkylbenzenesulfonic acid salt, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt and the like, but is not limited thereto.
- the crosslinking agent is, for example melamine type, a substituted urea, or a cross-linker having these can be given a polymer such as eu
- at least two cross-link the substituent for example, methoxy hydroxy methylated glycosides ruril, Appendix during methylation glycolate
- substituent for example, methoxy hydroxy methylated glycosides ruril, Appendix during methylation glycolate
- ruryl methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, annexed methylated benzoguanamine, methoxymethylated urea, annexed methylated urea, methoxymethylated thiourea, or an appendoxymethylated thiourea
- ruryl methoxymethylated melamine
- butoxymethylated melamine methoxymethylated benzoguanamine
- annexed methylated benzoguanamine methoxy
- a crosslinking agent having high heat resistance may be used as the crosslinking agent.
- the crosslinking agent having high heat resistance has an aromatic ring (for example, a benzene ring or a naphthalene ring) in the molecule.
- Compounds containing crosslinking substituents can be used.
- the thermal acid generators include, for example, P-luenesulfonic acid, trifluoromethanesulfonic acid, pyridinium P-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid,
- Acidic compounds such as hydroxybenzoic acid, naphthalenecarboxylic acid, and / or 2,4,4,6-tetrabromocyclonuxadienone, benzointosylate, 2-nitrobenzyltosylate, and other alkyl esters It may be used, but is not limited thereto.
- the additive may be included in an amount of about 0.001 to 40 parts by weight based on 100 parts by weight of the organic film composition. By including in the said range, solubility can be improved without changing the optical characteristic of an organic film composition.
- an organic film prepared using the organic film composition described above is provided.
- the organic layer may be in the form of the above-described organic layer composition, for example, coated on a substrate and cured through a heat treatment process, and may include, for example, an organic thin film used in an electronic device such as a hard mask layer, a planarization layer, a sacrificial layer, a layer release agent, and the like. I can do it
- a method of forming a pattern includes: providing a material layer on a substrate, applying an organic film composition including the polymer and a solvent on the material layer, and heat treating the organic film composition to form a hard mask layer. Forming a photoresist layer on the hard mask layer; exposing and developing the photoresist layer; forming a photoresist pattern by exposing and developing the photoresist layer; of
- 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, for example, a metal layer such as aluminum or copper, a semiconductor layer such as silicon, or an insulating layer such as silicon oxide, silicon nitride, or the like.
- the material layer can be formed, for example, by chemical vapor deposition.
- the organic film composition is as described above, it 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, and for example, may be applied to a thickness of about 50 to ⁇ .
- the heat treatment of the organic layer composition may be performed, for example, at about 100 to 500 ° C for about 10 seconds to 1 hour.
- the heat treatment may include a first heat treatment performed at 50 to 250 ° C, and a second heat treatment following the first heat treatment and proceeding at 200 to 500 ° C.
- the silicon-containing thin film layer may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, and / or SiN.
- a bottom anti-reflective coating may be further formed on the silicon-containing thin film layer before the forming of the photoresist layer.
- Exposing the photoresist layer may be performed using, for example, ArF, KrF or EUV.
- a heat treatment process may be performed at about 100 to 500 ° C after exposure.
- Etching the exposed portion of the material layer may be performed by dry etching using an etching gas, which may use, for example, CHF 3 , CF 4 , Cl 2 , BC1 3, and a combination thereof.
- an etching gas which may use, for example, CHF 3 , CF 4 , Cl 2 , BC1 3, and a combination 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, for example, various patterns in a semiconductor integrated circuit device.
- the molecular weight was confirmed by GPC to complete the reaction when the weight average molecular weight was 2,000 to 3,500.
- naphthalen-1-ol (10 g), l, 3-bis (4- (methoxymethyl) phenoxy) benzene (24.3 g),
- a polymer comprising a structural unit represented by the formula lg 'through 10 (C same synthesis as in Synthesis Example 1) using monomethyl ether acetate (PGMEA) (123 g) and diethylsulfate (0.5 g). (Mw: 3,300).
- naphthalen-1-ol (7.2 g), IH-indol (5.9 g), 4-hydroxy-1 -naphthaldehyde (17 g) propylene glycol monomethyl ether acetate (PGMEA) (129 g) and
- polymer lk containing the structural unit represented by general formula lk was obtained using the method similar to the resin polymerization of the synthesis example 1 in rc.
- Aqueous solution (0.75 g), H 2 O (1.5 g) and NaOH 10% (2.3 g) were added dropwise in order.
- the polymer and the additives were dissolved in a propylene glycol monomethyl ether acetate (PGMEA) solvent and filtered to prepare a hard mask composition.
- PGMEA propylene glycol monomethyl ether acetate
- composition of the polymer and the additive is shown in Table 1 below.
- the content of solids in the hard mask composition was adjusted so that the thickness of the composition on the bare wafer was 2000 A after the first heat treatment at 180 ° C. for 120 seconds and after the second heat treatment at 400 ° C. for 120 seconds.
- the hard mask composition was spin-on coated, and then the thin film was subjected to a first heat treatment at 180 ° C. for 120 seconds and then second heat treatment at 400 ° C. for 120 seconds.
- the planarization characteristic is observed by measuring the difference (that is, the step) between the film thicknesses of the resist underlayer film in the part with holes and without part.
- 1 is an enlarged cross-sectional view of an arbitrary pattern on a silicon wafer coated with a coating liquid. The thickness indicated by the arrow in FIG. 1 corresponds to the step.
- the planarization characteristic is excellent as the difference (step difference) between the film thickness of a part with a pattern and a part without a pattern is so large that a numerical value is so excellent that a planarization characteristic is excellent.
- the results are as shown in Table 2.
- the hard mask composition according to Examples 7 to 14 and Comparative Examples 1 and 3 on a silicon wafer was spin-on-coated the hard mask composition onto a 12 inch silicon wafer, and then the thin film was first heat-treated at 180 ° C. for 120 seconds. After the second heat treatment at 400 ° C for 120 seconds. After the second heat treatment, the solid content was adjusted so that the thickness of the thin film was 2,000 A.
- the thickness of the thin film after the second heat treatment is 2,000 A
- the thin film formed from the composition was superior in coating property as compared with the thin film formed from the hardmask compositions according to Comparative Examples 2 and 3.
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Abstract
The present invention relates to an organic film composition and a pattern formation method using same, the organic film composition comprising: a polymer comprising a structural unit represented by chemical formula 1; an additive which is an aromatic ring-containing compound comprising, in the structure thereof, at least one of a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group or a nitrile group; and a solvent. The definition of chemical formula 1 is as described in the specification.
Description
【명세서】 【Specification】
【발명의 명칭】 [Name of invention]
유기막 조성물 및 패턴형성방법 Organic film composition and pattern forming method
【기술분야】 Technical Field
유기막 조성물, 그리고 상기 유기막 조성물을 사용하여 패턴을 형성하는 방법에 관한 것이다. An organic film composition and the method of forming a pattern using the said organic film composition.
【배경기술】 Background Art
최근 일렉트로닉 디바이스의 소형화 (miniaturation) 및 복잡화 (complexity)에 따른 고집적 설계는 더욱 진보된 소재와 관련 공정의 개발을 가속화하고 있으며， 이에 따라 기존 포토레지스트를 이용한 리소그래피 역시 새로운 패터닝 소재와 기법들을 필요로 하게 되었다ᅳ In recent years, highly integrated designs due to miniaturization and complexity of electronic devices have accelerated the development of more advanced materials and related processes, and thus lithography using existing photoresists also requires new patterning materials and techniques. ᅳ
패터닝 공정에서 포토레지스트의 미세 패턴을 붕괴 현상 없이 충분한 깊이로 기판에 전사시키기 위하여 단단한 중간막인 일명 하드마스크 층 (hardmask layer)이라고 불리는 유기막을 형성할 수 있다. In the patterning process, in order to transfer the fine pattern of the photoresist to the substrate to a sufficient depth without collapse phenomenon, an organic film called a hard mask layer (hard mask layer) may be formed.
하드마스크 층은 선택적 식각 과정을 통하여 포토레지스트의 미세 패턴을 재료 층으로 전사해주는 중간막으로서 역할을 한다. 따라서 하드마스크 층은 다중 식각 과정 동안 견딜 수 있도록 내열성 및 내식각성 등의 특성이 필요하다. 한편, 근래 하드마스크 층은 화학기상증착 방법 대신 스핀-온 코팅 (spin-on coating) 방법으로 형성하는 것이 제안되었다. 스핀-온 코팅 방법은 공정이 용이할 뿐만 아니라 갭-필 (gap-fill) 특성 및 평탄화 특성을 개선할 수 있다. The hard mask layer serves as an interlayer that transfers the fine pattern of the photoresist to the material layer through a selective etching process. Therefore, the hard mask layer needs properties such as heat resistance and etching resistance to withstand multiple etching processes. On the other hand, it has recently been proposed that the hard mask layer is formed by a spin-on coating method instead of a chemical vapor deposition method. The spin-on coating method is not only easy to process but can also improve gap-fill and planarization properties.
일반적으로, 내열성 및 내식각성은 스핀-온 특성과 상충관계에 있어 이들 물성을 모두 만족할 수 있는 유기막 재료가 요구된다. In general, heat resistance and etching resistance are in conflict with spin-on characteristics, and an organic film material capable of satisfying both of these properties is required.
【발명의 상세한 설명】 [Detailed Description of the Invention]
【기술적 과제】 [Technical problem]
일 구현예는 스핀-온 방식으로 코팅 가능하면서도 내식각성이 우수한 유기막 조성물을 제공한다. One embodiment provides an organic film composition which can be coated in a spin-on manner and excellent in etching resistance.
다른 구현예는 상기 유기막 조성물을 사용한 패턴 형성 방법을 제공한다. 【기술적 해결방법】 Another embodiment provides a pattern forming method using the organic film composition. Technical Solution
일 구현예에 따르면, 하기 화학식 1로 표현되는 구조단위를 포함하는 중합체, 방향족 고리 함유 화합물로서 그 구조 내에 치환 또는 비치환된 아민기,
치환 또는 비치환된 비닐기 , 치환 또는비치환된 아세틸렌기 , 아자이드기 , 또는 나이트릴기를 적어도 하나 포함하는 첨가제, 그리고 용매를 포함하는 유기막 조성물을 제공한다. According to one embodiment, a polymer comprising a structural unit represented by the following formula (1), an aromatic ring-containing compound substituted or unsubstituted amine group in its structure, It provides an organic film composition comprising an additive comprising at least one substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, or a nitrile group, and a solvent.
[ 1]
[ One]
상기 화학식 1에서, In Chemical Formula 1,
A는 치환 또는 비치환된 방향족 고리 함유기， 치환 또는 비치환된 헤테로 방향족 고리 함유기, 또는 이들의 조합이고, A is a substituted or unsubstituted aromatic ring containing group, a substituted or unsubstituted hetero aromatic ring containing group, or a combination thereof,
B는 2가의 유기기이고， B is a divalent organic group,
A 및 B 중 적어도 하나는 하기 화학식 2로 표현되는 부분을 포함하는 작용기에 의해 치환된 것이다: At least one of A and B is substituted by a functional group comprising a moiety represented by the following formula (2):
[화학식 2] [Formula 2]
Z는 수소, 히드록시기， 치환 또는 비치환된 C 1 내지 C10 알킬기, 또는 치환 또는 비치환된 C6 내지 C30 아¾기이고, Z is hydrogen, a hydroxy group, a substituted or unsubstituted C 1 to C 10 alkyl group, or a substituted or unsubstituted C 6 to C 30 atom group,
*는 연결지점이다. * Is the connection point.
상기 화학식 2로 표현되는 부분을 포함하는 작용기는 하기 화학식 2'로 표현되는 것일 수 있다.
[화학식 2'] The functional group including the moiety represented by Formula 2 may be represented by the following Formula 2 '. [Formula 2 ']
상기 화학식 2'에서， In Chemical Formula 2 ',
W는 0, S, NRa또는 CRbRc이고, 여기서 Ra 내지 Rc는 각각 독립적으로 수소 치환 또는 비치환된 C1 내지 C10 알킬기, 할로겐 원자, 할로겐 함유기 또는 이들의 조합이고， W is 0, S, NR a or CR b R c , wherein R a to R c are each independently a hydrogen substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group or a combination thereof,
Z는 수소, 히드록시기, 치환 또는 비치환된 C1 내지 C10 알킬기, 또는 치환 또는 비치환된 C6 내지 C30 아릴기이고, Z is hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
a는 0 또는 1이고, a is 0 or 1,
b는 0 내지 10의 정수이고, b is an integer from 0 to 10,
*는 연결지점이다. * Is the connection point.
상기 첨가제는 하기 화학식 3으로 표현될 수 있다. The additive may be represented by the following formula (3).
[화학식 3] [Formula 3]
(R)k^ R')m ( R ) k ^ R ') m
상기 화학식 3에서, In Chemical Formula 3,
k, m 및 n는 각각 독립적으로 0 또는 1이되 k, m 및 n의 합은 2 또는 3이고 k+m+n=3일 때 X는 -CH- 또는 질소 (N)이고, k, m and n are each independently 0 or 1, and the sum of k, m and n is 2 or 3 and when k + m + n = 3, X is -CH- or nitrogen (N),
k+m+n=2일 때 X는 직접결합, -(CqH2q)-, -(CtRw 2t)-, 산소 (0), 황 (S), -NH-, 또는 -S(02)-이고, 여기서 q 및 t는 각각 독립적으로 1 내지 5인 정수이고 Rw는 치환 또는 비치환된 C1 내지 C20 알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기，
치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C 1 내지 C20 알킬아민기, 치환 또는 비치환된 C7 내지 C20 아릴알킬기, 치환 또는 비치환된 C 1 내지 C20 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 When k + m + n = 2, X is a direct bond,-(C q H 2q )-,-(C t R w 2t )-, oxygen (0), sulfur (S), -NH-, or -S (0 2 )-, wherein q and t are each independently an integer of 1 to 5 and R w is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, Substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C 1 to C20 alkylamine group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted C 1 to C20 heteroalkyl group, substituted or Unsubstituted C2 to C30
헤테로사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C 1 내지 C4 알킬 에테르기， 치환 또는 비치환된 C7 내지 C20 아릴알킬렌 에테르기， 치환 또는 비치환된 C 1 내지 C30 할로알킬기, 치환 또는 비치환된 C2 내지 C20 알케닐기, 또는 이들의 조합이고,Heterocycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C 1 to C4 alkyl ether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C 1 To C30 haloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,
, R'및 R"는 각각 독립적으로 치환 또는 비치환된 방향족 고리 함유기이되 R, R'또는 R" 는 치환 또는 비치환된 아민기, 치환 또는 비치환된 비닐기, 치환 또는 비치환된 아세틸렌기, 아자이드기, 또는 나이트릴기를 적어도 하나 포함한다. 상기 첨가제는 하기 화학식 4 또는 5로 표현될 수 있다. , R 'and R "are each independently a substituted or unsubstituted aromatic ring containing group, R, R' or R" is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene At least one group, azide group, or nitrile group. The additive may be represented by the following formula (4) or (5).
[화학식 4] [Formula 4]
1
One
[화학식 5] [Formula 5]
상기 화학식 4 및 5에서, In Chemical Formulas 4 and 5,
X1는 -CH- 또는 질소 (N)이고, X 1 is -CH- or nitrogen (N),
X2는 직접결합, -(CqH2q)-, -(CtRw 2t)-, 산소 (0), 황 (S), -NH- 또는 -S(02)-이고, 여기서 q 및 t는 각각 독립적으로 1 내지 5인 정수이고 Rw는 치환 또는 비치환된 C 1 내지 C20 알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C 1 내지 C20 알킬아민기, 치환 또는 비치환된 C7 내지 C20 아릴알킬기, 치환 또는 비치환된 C 1 내지 C20 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 X 2 is a direct bond,-(C q H 2q )-,-(C t R w 2t )-, oxygen (0), sulfur (S), -NH- or -S (0 2 )-, wherein q And t are each independently an integer of 1 to 5 and R w is a substituted or unsubstituted C 1 to C20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 3 to C 30 cycloalkenyl group, substituted Or an unsubstituted C 1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C 1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30
헤테로사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C1 내지 C4 알킬 에테르기， 치환 또는 비치환된 C7 내지 C20 아릴알킬렌 에테르기, 치환 또는 비치환된 C 1 내지 C30 할로알킬기, 치환 또는
비치환된 C2 내지 C20 알케닐기, 또는 이들의 조합이고， Heterocycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C1 to C4 alkyl ether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C 1 to C30 haloalkyl group, substituted or Unsubstituted C2 to C20 alkenyl group, or a combination thereof,
R1 내지 R5는 각각 독립적으로 하기 화학식 6으로 표현되는 기를 적어도 하나 포함하는 방향족 고리 함유기이다: R 1 to R 5 are each independently an aromatic ring-containing group including at least one group represented by the following formula (6):
[화학식 6] [Formula 6]
( )a () a
상기 화학식 6에서, In Chemical Formula 6,
W는 0, S, NRa또는 CRbRc이고, 여기서 Ra 내지 Rc는 각각 독립적으로 수소 치환 또는 비치환된 C1 내지 C10 알킬기, 할로겐 원자， 할로겐 함유기 또는 이들의 조합이고, W is 0, S, NR a or CR b R c , wherein R a to R c are each independently a hydrogen substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group or a combination thereof,
Y는 치환 또는 비치환된 아민기 , 치환 또는 비치환된 비닐기 , 치환 또는 비치환된 아세틸렌기 , 아자이드기, 나이트릴기, 또는 이들의 조합이고, Y is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, a nitrile group, or a combination thereof,
a는 0 또는 1이고, a is 0 or 1,
b는 0 내지 10의 정수이고, b is an integer from 0 to 10,
*는 연결지점이다. * Is the connection point.
상기 화학식 4 및 5에서, R1 내지 R5는 각각 독립적으로 하기 화학식 7로 표현될 수 있다. In Chemical Formulas 4 and 5, R 1 to R 5 may be each independently represented by the following Chemical Formula 7.
[화학식 7] [Formula 7 ]
Rla 내지 Rl3a은 각각 독립적으로 수소, 히드록시기, 치환 또는 비치환된 C1 내지 C10 알킬기, 또는 상기 화학식 6으로 표시되는 기이되, Rla 내지 R13a중
적어도 하나는 상기 화학식 6으로 표시되는 기이고， R la to R l3a are each independently hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, or a group represented by Formula 6, wherein R la to R 13a At least one is a group represented by the formula (6),
T1 및 T2는 각각 독립적으로 0, S, NRa 또는 CRbRc이고, 여기서 Ra 내지 ^는 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 할로겐 원자, 할로겐 함유기 또는 이들의 조합이고, T 1 and T 2 are each independently 0, S, NR a or CR b R c , wherein R a to ^ are each independently hydrogen, a substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group or Combination of these,
c 및 d는 각각 독립적으로 0 내지 5인 정수이고, c and d are each independently an integer of 0 to 5,
*는 연결지점이다. * Is the connection point.
상기 화학식 1에서, 상기 A는 하기 그룹 1 및 2 중에서 선택된 치환 또는 비치환된 모이어티일 수 있다. In Formula 1, A may be a substituted or unsubstituted moiety selected from the following groups 1 and 2.
[그룹 1] [Group 1]
[그 [That
상기 그룹 2에서, In group 2 above,
Z1 및 Z2는 각각 독립적으로 NRd, 0, S, Te 또는 Se이고, Z 1 and Z 2 are each independently NR d , 0, S, Te or Se,
Z3 및 Z4는 N이고, Z 3 and Z 4 are N,
Rd 및 Re은 각각 독립적으로 수소, 히드록시기, 메록시기, 에특시기, 할로겐 원자， 할로겐 함유기, 치환 또는 비치환된 1 내지 C30 알킬기, 치환 또는 R d and R e are each independently hydrogen, a hydroxy group, a hydroxy group, a special group, a halogen atom, a halogen-containing group, a substituted or unsubstituted 1 to C30 alkyl group, a substituted or
비치환된 C6 내지 C30 아릴기, 또는 이들의 조합이다. Unsubstituted C6 to C30 aryl groups, or a combination thereof.
상기 화학식 1에서, 상기 A는 적어도 1개의 치환 또는 비치환된 방향족， 헤테로 방향족 고리를 포함할 수 있다. In Formula 1, A may include at least one substituted or unsubstituted aromatic or heteroaromatic ring.
상기 B는 하기 화학식 Z1 내지 화학식 Z4 중 어느 하나로 표현될 수 있다. B may be represented by any one of Formulas Z1 to Z4.
[화학식 Z1
[Formula Z1
[화학식 Ζ2]
[Formula Ζ2]
ᅴ훼 4
[화학식 Z3]
ᅴ fe 4 [Formula Z3]
H H
[ Z4]
[Z4]
상기 화학식 Z1 내지 Z4에서, In Chemical Formulas Z1 to Z4,
e 및 f는 각각 독립적으로 0 또는 1이고, e and f are each independently 0 or 1,
g는 1 내지 5인 정수이고, g is an integer of 1 to 5,
Y1내지 Y4는 각각 독립적으로 하기 그룹 3에서 선택된 치환 또는 비치환된 모이어티 중 어느 하나이고, Y 1 to Y 4 are each independently any one of a substituted or unsubstituted moiety selected from Group 3,
*은 연결지점이다: * Is the connection point:
[그룹 3] [Group 3]
M, M'및 M"는 각각 독립적으로 치환 또는 비치환된 C1 내지 C10 알킬렌기, 0, S, S02, CRfRg, NRh, 또는 카르보닐이고， 여기서 Rf 내지 Rh는 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 할로겐 원자, 할로겐 함유기 또는 이들의 조합이고, M, M 'and M "are each independently a substituted or unsubstituted C1 to C10 alkylene group, 0, S, S0 2 , CR f R g , NR h , or carbonyl, wherein R f to R h are each Independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen containing group or a combination thereof,
L1은 치환 또는 비치환된 C6 내지 C50 아릴렌기, 치환 또는 비치환된 C1 내지 C10 알킬렌옥사이드 함유기, 또는 이들의 조합이고， L 1 is a substituted or unsubstituted C6 to C50 arylene group, a substituted or unsubstituted C1 to C10 alkylene oxide containing group, or a combination thereof,
r은 0 내지 10인 정수이고, r is an integer from 0 to 10,
s는 0 내지 10인 정수이고, s is an integer from 0 to 10,
k는 0 내지 3인 정수이다. k is an integer of 0-3.
상기 중합체는 하기 화학식 8로 표현되는 구조단위를 더 포함할 수 있다. The polymer may further include a structural unit represented by the following Chemical Formula 8.
[화학식 8]
상기 화학식 8에서, [Formula 8] In Chemical Formula 8,
X0는 치환 또는 비치환된 방향족 고리 함유기, 치환 또는 비치환된 헤테로 방향족 고리 함유기, 또는 이들의 조합이고, X 0 is a substituted or unsubstituted aromatic ring containing group, a substituted or unsubstituted hetero aromatic ring containing group, or a combination thereof,
L0은 2가의 유기기이고, L 0 is a divalent organic group,
*은 연결지점이다. * Is the connection point.
상기 화학식 8에서 상기 X0는 하기 그룹 1 및 2 중에서 선택된 치환 또는 비치환된 모이어티일 수 있다.
In Formula 8, X 0 may be a substituted or unsubstituted moiety selected from Groups 1 and 2 below.
상기 그룹 2에서， In group 2 above,
Z' 및 Z2는 각각 독립적으로 NRd，ᄋ, S, Te 또는 Se이고, Z 'and Z 2 are each independently NR d , 0, S, Te or Se,
Z3 및 Z4는 N이고， Z 3 and Z 4 are N,
Rd 및 Re은 각각 독립적으로 수소, 히드록시기, 메록시기, 에록시기, 할로겐 원자， 할로겐 함유기， 치환 또는 비치환된 1 내지 C30 알킬기， 치환 또는
비치환된 C6 내지 C30 아릴기, 또는 이들의 조합이다. R d and R e are each independently hydrogen, hydroxy group, hydroxy group, hydroxy group, halogen atom, halogen containing group, substituted or unsubstituted 1 to C30 alkyl group, substituted or Unsubstituted C6 to C30 aryl groups, or a combination thereof.
상기 중합체는 그 구조단위 내에 적어도 하나의 산소 원자를 포함할 수 있다. The polymer may contain at least one oxygen atom in its structural unit.
상기 화학식 2는 하기 화학식 2'로 표현될 수 있다. Formula 2 may be represented by the following formula (2 ').
[화학식 2'] [Formula 2 ']
(W)a (W) a
상기 화학식 2'에서, In Chemical Formula 2 ',
W는 0, S, NRa또는 CRbRc이고, 여기서 Ra 내지 ！ 는 각각 독립적으로 수소 치환 또는 비치환된 C1 내지 C20 알킬기, 할로겐 원자， 할로겐 함유기 또는 이들의 조합이고, W is 0, S, NR a or CR b R c , wherein R a to! Are each independently a hydrogen substituted or unsubstituted C 1 to C 20 alkyl group, a halogen atom, a halogen containing group or a combination thereof,
a는 0 또는 1이고, a is 0 or 1,
*는 연결지점이다. * Is the connection point.
상기 첨가제는 하기 화학식 Y1 내지 Y4 중 어느 하나로 표현될 수 있다. [화학식 Yi] The additive may be represented by any one of the following formulas Y1 to Y4. [Formula Yi]
[화학식 Y4] [Formula Y4]
상기 화학식 Y1 내지 Υ4에서, In Chemical Formulas Y1 to V4,
Τ3 및 Τ4는 각각 독립적으로 0, S, NRa또는 CRbRc이고, 여기서 Ra 내지 R c는 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 할로겐 원자, 할로겐 함유기 또는 이들의 조합이고, Τ 3 and Τ 4 are each independently 0, S, NR a or CR b R c , wherein R a to R c are each independently hydrogen, a substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group Or a combination thereof,
Rx 내지 Ry는 각각 독립적으로 수소, 할로겐 원자, 할로겐 함유기, 또는 치환 또는 비치환된 C1 내지 C20 알킬기이고, R x to R y are each independently hydrogen, a halogen atom, a halogen-containing group, or a substituted or unsubstituted C1 to C20 alkyl group,
R33 내지 R55은 각각 독립적으로 하기 화학식 6으로 표시되는 기이다: R 33 to R 55 are each independently a group represented by the following formula (6):
[화학식 6] [Formula 6]
(W)a (W) a
상기 화학식 6에서, In Chemical Formula 6,
W는 0, S, NRa또는 CRbRc이고, 여기서 Ra 내지 Rc는 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 할로겐 원자, 할로겐 함유기 또는 이들의 조합이고, W is 0, S, NR a or CR b R c , wherein R a to R c are each independently hydrogen, a substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group or a combination thereof,
Y는 치환 또는 비치환된 아민기, 치환 또는 비치환된 비닐기, 치환 또는 비치환된 아세틸렌기, 아자이드기, 나이트릴기, 또는 이들의 조합이고,
a는 0 또는 1이고, Y is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, a nitrile group, or a combination thereof, a is 0 or 1,
b는 0 내지 10의 정수이고, b is an integer from 0 to 10,
*는 연결지점이다. * Is the connection point.
상기 첨가제는 150 내지 50,000의 분자량올 가질 수 있다. The additive may have a molecular weight of 150 to 50,000.
상기 중합체는 500 내지 200,000의 중량평균분자량을 가질 수 있다. The polymer may have a weight average molecular weight of 500 to 200,000.
상기 첨가제는 상기 유기막 조성물의 총 함량에 대하여 5 중량0 /。 내지 50 중량 %로 포함될 수 있다. The additive may comprise from 5 parts by weight 0 /. To 50% by weight, based on the total amount of the organic film composition.
다른 구현예에 따르면, 기판 위에 재료 층을 제공하는 단계, 상기 재료 층 위에 상술한 유기막 조성물을 적용하는 단계, 상기 유기막 조성물을 열처리하여 하드마스크 층을 형성하는 단계， 상기 하드마스크 층 위에 실리콘 함유 박막층을 형성하는 단계, 상기 실리콘 함유 박막층 위에 포토레지스트 층을 형성하는 단계， 상기 포토레지스트 층을 노광 및 현상하여 포토레지스트 패턴을 형성하는 단계, 상기 포토레지스트 패턴을 이용하여 상기 실리콘 함유 박막층 및 상기 According to another embodiment, a step of providing a material layer on a substrate, applying the organic film composition described above on the material layer, heat treating the organic film composition to form a hard mask layer, silicon on the hard mask layer Forming a 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, using the photoresist pattern and the silicon containing thin film layer and the
하드마스크 층을 선택적으로 제거하고 상기 재료 층의 일부를 노출하는 단계, 그리고 상기 재료 층의 노출된 부분을 식각하는 단계를 포함하는 패턴 형성 방법을 제공한다. Selectively removing the hardmask layer, exposing a portion of the material layer, and etching the exposed portion of the material layer.
상기 유기막 조성물을 적용하는 단계는 스핀-온 코팅 방법으로 수행할 수 있다. 상기 열처리는 50 내지 250 °C에서 진행되는 제 1차 열처리, 그리고 상기 제 1 열처리에 후속되고 200 내지 500 °C에서 진행되는 제 2차 열처리를 포함할 수 있다. Applying the organic film composition may be performed by a spin-on coating method. The heat treatment may include a first heat treatment performed at 50 to 250 ° C., and a second heat treatment following the first heat treatment and performed at 200 to 500 ° C.
상기 포토레지스트 층을 형성하는 단계 전에 바닥 반사 방지 층 (BARC)을 형성하는 단계를 더 포함할 수 있다. The method may further include forming a bottom anti-reflection layer (BARC) before forming the photoresist layer.
【발명의 효과】 【Effects of the Invention】
소정의 중합체와 소정의 첨가제를 포함함으로써 스핀-온 방식으로 코팅 가능하면서도 내식각성이 우수한 유기막 조성물을 제공한다. 상기 유기막 조성물로부터 제조된 유기막은 막 밀도 및 막 평탄성이 모두 우수하다. By including the predetermined polymer and the predetermined additive, it is possible to provide an organic film composition which can be coated in a spin-on manner and excellent in etching resistance. The organic film prepared from the organic film composition is excellent in both film density and film flatness.
【도면의 간단한 설명】 [Brief Description of Drawings]
도 1은 평탄화 특성 (단차 특성)을 평가하는 방법을 설명하기 위한 도면이고, 도 2는 두께 유니포미티 (Thickness Uniformity) 특성의 평가 방법을 설명하기 위한 도면이다.
【발명을 실시하기 위한 최선의 형태】 FIG. 1 is a diagram for explaining a method for evaluating flattening characteristics (difference characteristics), and FIG. 2 is a diagram for explaining a method for evaluating thickness uniformity characteristics. [The best form to carry out invention]
이하, 본 발명의 구현예에 대하여 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 구현예에 한정되지 않는다. Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.
본 명세서에서 별도의 정의가 없는 한，'치환된'이란, 화합물 중의 수소 원자가 할로겐 원자 (F, Br, Cl, 또는 1)， 히드록시기, 알콕시기, 니트로기， 시아노기， 아미노기 , 아지도기， 아미디노기 , 히드라지노기 , 히드라조노기 , 카르보닐기, 카르바밀기, 티을기 , 에스테르기 , 카르복실기나 그의 염 , 술폰산기나 그의 염 , 인산이나 그의 염， C1 내지 C20 알킬기， C2 내지 C20 알케닐기， C2 내지 C20 알키닐기， C6 내지 C30 아릴기, C7 내지 C30 아릴알킬기, C 1 내지 C30 알콕시기, C1 내지 C20 헤테로알킬기, C2 내지 C20 헤테로아릴기, C3 내지 C20 Unless otherwise defined herein, "substituted" means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl, or 1), hydroxy group, alkoxy group, nitro group, cyano group, amino group, azido group, amine Dino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thi group, ester group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 To C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C 1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C2 to C20 heteroaryl group, C3 to C20
헤테로아릴알킬기， C3 내지 C30 사이클로알킬기, C3 내지 C15의 사이클로알케닐기 C6 내지 C15 사이클로알키닐기, C2 내지 C30 헤테로사이클로알킬기 및 이들의 조합에서 선택된 치환기로 치환된 것을 의미한다. It means substituted by a substituent selected from a heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C30 heterocycloalkyl group, and a combination thereof.
또한, 본 명세서에서 별도의 정의가 없는 한, '헤테로 '란， N, 0, S 및 P에서 선택된 헤테로 원자를 1 내지 3개 함유한 것을 의미한다. In addition, unless otherwise defined herein, "hetero" means containing 1 to 3 heteroatoms selected from N, 0, S and P.
이하 일 구현예에 따른 유기막 조성물을 설명한다. Hereinafter, an organic film composition according to an embodiment will be described.
일 구현예에 따른 유기막 조성물은 하기 화학식 1로 표현되는 구조단위를 포함하는 중합체, 방향족 고리 함유 화합물로서 치환 또는 비치환된 아민기, 치환 또는 비치환된 비닐기, 치환 또는 비치환된 아세틸렌기, 아자이드기, 또는 나이트릴기를 적어도 하나 포함하는 첨가제, 그리고 용매를 포함하는 유기막 조성물올 제공한다. The organic film composition according to the embodiment is a polymer comprising a structural unit represented by the following formula (1), a substituted or unsubstituted amine group as an aromatic ring-containing compound, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group It provides an organic film composition comprising an additive comprising at least one, an azide group, or a nitrile group, and a solvent.
[ 1]
[ One]
상기 화학식 1에서， In Chemical Formula 1,
A는 치환 또는 비치환된 방향족 고리 함유기, 치환 또는 비치환된 헤테로 방향족 고리 함유기, 또는 이들의 조합이고, A is a substituted or unsubstituted aromatic ring containing group, a substituted or unsubstituted hetero aromatic ring containing group, or a combination thereof,
B는 2가의 유기기이고,
A 및 B 중 적어도 하나는 하기 화학식 2로 표현되는 부분을 포함하는 작용기에 의해 치환된 것이다: B is a divalent organic group, At least one of A and B is substituted by a functional group comprising a moiety represented by the following formula (2):
[화학식 2] [Formula 2]
Z는 수소, 히드록시기, 치환 또는 비치환된 C1 내지 C10 알킬기, 또는 치환 또는 비치환된 C6 내지 C30 아릴기이고, Z is hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
*는 연결지점이다. * Is the connection point.
상기 유기막 조성물은 소정 구조의 중합체 및 소정 구조의 첨가제를 포함한다. 먼저, 상기 중합체에 관하여 설명한다. The organic film composition includes a polymer having a predetermined structure and an additive having a predetermined structure. First, the said polymer is demonstrated.
상기 중합체는 상기 화학식 1로 표현되는 구조단위를 1종 또는 2종 이상 ' 포함하며, 상기 그 구조 단위 내에 A로 표현되는 방향족 고리기 함유 부분 및 B로 표현되는 연결기 부분을 포함한다. The polymer comprises a connector portion, and a structural unit containing alone or in combination of two or more, which is represented by the formula 1, represented as B-containing portion and an aromatic group represented by A in the above structural units.
일 예로, 상기 A는 치환 또는 비치환된 방향족 고리 함유기일 수 있으며， 예컨대 하기 그룹 1에서 선택된 치환 또는 비치환된 모이어티를 포함할 수 있으나, 이에 한정되는 것은 아니다.
For example, A may be a substituted or unsubstituted aromatic ring-containing group, and may include, for example, a substituted or unsubstituted moiety selected from Group 1, but is not limited thereto.
[그룹 1] [Group 1]
a8 翁 a8 翁
门 r~i门 r ~ i
[그룹 2] [Group 2]
Ά쎄:) 상기 그룹 2에서, Ά:: In group 2 above,
Ζ1 및 Ζ2는 각각 독립적으로 NRd, 0, S, Te 또는 Se이고, Ζ 1 and Ζ 2 are each independently NR d , 0, S, Te, or Se,
Z3 및 Z4는 N이고,
Rd 및 Re은 각각 독립적으로 수소， 히드록시기, 메톡시기, 에톡시기， 할로겐 원자, 할로겐 함유기, 치환 또는 비치환된 1 내지 C30 알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 또는 이들의 조합이다. Z 3 and Z 4 are N, R d and R e are each independently hydrogen, hydroxy group, methoxy group, ethoxy group, halogen atom, halogen containing group, substituted or unsubstituted 1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, or their It is a combination.
또 다른 일 예로, 상기 A는 치환 또는 비치환된 방향족 고리 함유기, 그리고 치환 또는 비치환된 헤테로 방향족 고리 함유기의 조합일 수도 있다.예를 들어 , 상기 화학식 1에서 A는 2개 이상의 치환 또는 비치환된 벤젠 고리를 포함할 수 있고， 예컨대 2개 내지 6개의 치환 또는 비치환된 벤젠 고리를 포함할 수 있다. 여기서 상기 벤젠 고리는 적어도 하나의 히드록시기에 의해 치환된 것일 수 있다. As another example, A may be a combination of a substituted or unsubstituted aromatic ring-containing group, and a substituted or unsubstituted hetero aromatic ring-containing group. For example, in Formula 1, A may be two or more substituted or It may comprise an unsubstituted benzene ring, for example two to six substituted or unsubstituted benzene rings. Here, the benzene ring may be substituted by at least one hydroxy group.
상기 화학식 1에서 연결기를 나타내는 B는 2가의 유기 선형기 , 2가의 유기 고리기, 또는 이들의 조합일 수 있다. 예를 들어， 상기 B는 하기 화학식 Z1 내지 화학식 Z4 중 어느 하나로 표현될 수 있으나, 이에 한정되는 것은 아니다. B representing the linking group in Chemical Formula 1 may be a divalent organic linear group, a divalent organic ring group, or a combination thereof. For example, B may be represented by any one of Formulas Z1 to Z4, but is not limited thereto.
[화학식 Z1] [Formula Z1]
. _ c 느 γ ' " . . γ c γ '".
[화학식 Z2
[Formula Z 2
I I
γ3 γ 3
[화학식 Ζ3] [Formula Ζ3]
Υ4
Υ 4
H H
[ Z4]
[Z4]
상기 화학식 zi 내지 Z4에서, In Chemical Formulas zi to Z4,
e 및 f는 각각 독립적으로 0 또는 1이고
g는 1 내지 5인 정수이고， e and f are each independently 0 or 1 g is an integer of 1 to 5,
Y1내지 Y4는 각각 독립적으로 하기 그룹 3에서 선택된 치환 또는 비치환된 모이어티 중 어느 하나이고, Y 1 to Y 4 are each independently any one of a substituted or unsubstituted moiety selected from Group 3,
*은 연결지점이다: * Is the connection point:
[그룹 3] [Group 3]
M, M'및 M"는 각각 독립적으로 치환 또는 비치환된 C1 내지 C10 알킬렌기 0, S, S02, CRfRg, NRh, 또는 카르보닐이고, 여기서 Rf 내지 Rh는 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 할로겐 원자, 할로겐 함유기 또는 이들의 조합이고, M, M 'and M "are each independently a substituted or unsubstituted C1 to C10 alkylene group 0, S, S0 2 , CR f R g , NR h , or carbonyl, wherein R f to R h are each independently Hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof,
L1은 치환 또는 비치환된 C6 내지 C50 아릴렌기， 치환 또는 비치환된 C1 내지 C10 알킬렌옥사이드 함유기, 또는 이들의 조합이고, L 1 is a substituted or unsubstituted C6 to C50 arylene group, a substituted or unsubstituted C1 to C10 alkylene oxide containing group, or a combination thereof,
r은 0 내지 10인 정수이고， r is an integer from 0 to 10,
s는 3 내지 10인 정수이고, s is an integer of 3 to 10,
k는 1 내지 3인 정수이다.
한편, 상기 화학식 1에서, 상기 A 및 B 중 적어도 하나는 상기 화학식 2로 표현되는 아세틸렌 함유기에 의해 치환된다. 예를 들어， 상기 A로 표현되는 방향족 고리 함유기 또는 해테로 방향족 고리 함유기가 아세틸렌 함유기에 의해 치환되거나, 상기 B로 표현되는 연결기가 아세틸렌 함유기에 의해 치환되거나, 상기 A 부분 및 B 부분 모두가 아세틸렌 함유기에 의해 치환될 수 있다. 이 때， 치환 수는 특별히 한정되지 않는다. k is an integer of 1 to 3. In Formula 1, at least one of A and B is substituted by an acetylene-containing group represented by Formula 2. For example, the aromatic ring-containing group or the heteroaromatic ring-containing group represented by A may be substituted by an acetylene-containing group, the linking group represented by B may be substituted by an acetylene-containing group, or both the A and B portions may be acetylene. It may be substituted by the containing group. At this time, the number of substitutions is not particularly limited.
예를 들어， 상기 화학식 2로 표현되는 부분을 포함하는 작용기는 하기 화학식 2'로 표현되는 기일 수 있으나, 이에 한정되는 것은 아니다. For example, the functional group including the moiety represented by Chemical Formula 2 may be a group represented by Chemical Formula 2 ', but is not limited thereto.
[화학식 2'] [Formula 2 ']
(W)a (W) a
상기 화학식 2'에서, In Chemical Formula 2 ',
W는 0, S, NRa 또는 CRbR^l고, 여기서 Ra 내지 ！ 는 각각 독립적으로 수소 치환 또는 비치환된 C 1 내지 C10 알킬기, 할로겐 원자, 할로겐 함유기 또는 이들의 조합이고， W is 0, S, NR a or CR b R ^ l, wherein R a to! Are each independently a hydrogen substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group, or a combination thereof,
Z는 수소, 히드록시기, 치환 또는 비치환된 C1 내지 C10 알킬기, 또는 치환 또는 비치환된 C6 내지 C30 아릴기이고， Z is hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
a는 0 또는 1이고, a is 0 or 1,
b는 0 내지 10의 정수이고, b is an integer from 0 to 10,
*는 연결지점이다. * Is the connection point.
예를 들어， 상기 화학식 2로 표현되는 부분을 포함하는 작용기는 하기 화학식 2" 로 표현되는 기일 수 있으나, 이에 한정되는 것은 아니다.
[화학식 2"] For example, the functional group including the moiety represented by Formula 2 may be a group represented by Formula 2 ″, but is not limited thereto. [Formula 2 "]
(W)a (W) a
상기 화학식 2"에서, In Chemical Formula 2 ",
W는 0, S, NRa 또는 CRbRc이고, 여기서 Ra 내지 Rc는 각각 독립적으로 수소: 치환 또는 비치환된 C1 내지 C20 알킬기， 할로겐 원자, 할로겐 함유기 또는 이들의 조합이고, W is 0, S, NR a or CR b R c , wherein R a to R c are each independently hydrogen : a substituted or unsubstituted C 1 to C 20 alkyl group, a halogen atom, a halogen containing group or a combination thereof,
a는 0 또는 1이고, a is 0 or 1,
*는 연결지점이다. * Is the connection point.
예를 들어, 상기 중합체는 그 구조 내에 적어도 하나의 산소 원자를 포함할 수 있다. For example, the polymer may include at least one oxygen atom in its structure.
상기 중합체는 그 구조단위 내에 상기 A로 표현되는 방향족 고리 함유기， 또는 헤테로 방향족 고리 함유기를 포함함으로써 내식각성을 확보할 수 있고, 상기 B로 표현되는 유기기를 포함함으로써 유연성 (flexibility)를 확보할 수 있다. 또한, 상기 A 또는 B에 적어도 하나의 아세틸렌을 도입함으로써 상기 중합체가 경화될 때 상기 아세틸렌이 링 구조를 형성하게 됨으로써 중합체의 내식각성을 더욱 향상시킬 수 있다. 이에 따라 상기 중합체를 사용하여 형성된 유기막은 막 밀도가 우수하다. 뿐만 아니라, 상기 중합체를 사용하여 형성된 유기막은 두께 균일성 (uniformity)도 확보할 수 있다. The polymer can secure etch resistance by including the aromatic ring-containing group or heteroaromatic ring-containing group represented by A in the structural unit, and flexibility by securing the organic group represented by B. have. In addition, by introducing at least one acetylene to the A or B, the acetylene forms a ring structure when the polymer is cured, thereby further improving the etching resistance of the polymer. Accordingly, the organic film formed by using the polymer is excellent in film density. In addition, the organic film formed by using the polymer can ensure thickness uniformity.
상기 중합체는 예컨대 하기 화학식 8로 표현되는 구조단위를 더 포함할 수 있다. For example, the polymer may further include a structural unit represented by the following Chemical Formula 8.
[화학식 8] [Formula 8]
— 乂 ―. — 乂 ―.
상기 화학식 8에서,
X0는 치환 또는 비치환된 방향족 고리 함유기， 치환 또는 비치환된 헤테로 방향족 고리 함유기, 또는 이들의 조합이고, In Chemical Formula 8, X 0 is a substituted or unsubstituted aromatic ring containing group, a substituted or unsubstituted hetero aromatic ring containing group, or a combination thereof,
L0은 2가의 유기기이고, L 0 is a divalent organic group,
*은 연결지점이다. * Is the connection point.
상기 화학식 8에서 상기 X는 상기 그룹 1 및 2 중에서 선택된 치환 또는 비치환된 모이어티일 수 있고, 상기 L0은 연결기로서 상기 화학식 1의 Β에서 설명한 바와 같다. 다만， 상기 화학식 8로 표현되는 구조단위는 상기 화학식 1로 표현되는 구조단위와는 달리 아세틸렌 작용기를 필수적으로 포함하는 것은 아니다. In Formula 8, X may be a substituted or unsubstituted moiety selected from Groups 1 and 2, and L 0 is as described for Β of Formula 1 as a linking group. However, unlike the structural unit represented by Chemical Formula 1, the structural unit represented by Chemical Formula 8 does not necessarily include an acetylene functional group.
이하 상기 유기막 조성물에 포함되는 첨가제에 관하여 설명한다. Hereinafter, the additive contained in the organic film composition will be described.
상기 첨가제는 상술한 바와 같이 방향족 고리 함유 화합물로서 치환 또는 비치환된 아민기， 치환 또는 비치환된 비닐기, 치환 또는 비치환된 아세틸렌기, 아자이드기, 또는 나이트릴기를 적어도 하나 포함한다. As described above, the additive includes at least one substituted or unsubstituted amine group, substituted or unsubstituted vinyl group, substituted or unsubstituted acetylene group, azide group, or nitrile group as the aromatic ring-containing compound.
예를 들어， 상기 첨가제는 하기 화학식 3으로 표현될 수 있다. For example, the additive may be represented by the following formula (3).
[화학식 3] [Formula 3]
(R) k iR')m (R) k iR ') m
X X
( ")n (") n
상기 화학식 3에서, In Chemical Formula 3,
k, m 및 n는 각각 독립적으로 0 또는 1이되 k, m 및 n의 합은 2 또는 3이고, k+m+n=3일 때 X는— CH- 또는 질소 (N)이고, k, m and n are each independently 0 or 1, the sum of k, m and n is 2 or 3, and when k + m + n = 3, X is — CH— or nitrogen (N),
k+m+n=2일 때 X는 직접결합, -(CqH2q)-, -(CtRw 2t)-, 산소 (0), 황 (S), -NH-, 또는when k + m + n = 2, X is a direct bond,-(C q H 2q )-,-(C t R w 2t )-, oxygen (0), sulfur (S), -NH-, or
-S(02)-이고, 여기서 q 및 t는 각각 독립적으로 1 내지 5인 정수이고 ^는 치환 또는 비치환된 C 1 내지 C20 알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C 1 내지 C20 알킬아민기, 치환 또는 비치환된 C7 내지 C20 아릴알킬기, 치환 또는 -S (0 2 )-, wherein q and t are each independently an integer of 1 to 5, ^ is a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, substituted or unsubstituted A substituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C 1 to C20 alkylamine group, a substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or
비치환된 C 1 내지 C20 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 Unsubstituted C 1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30
헤테로사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C 1 내지 C4 알킬 에테르기， 치환 또는 비치환된 C7 내지 C20
아릴알킬렌 에테르기 , 치환 또는 비치환된 C1 내지 C30 할로알킬기, 치환 또는 비치환된 C2 내지 C20 알케닐기 , 또는 이들의 조합이고,Heterocycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C 1 to C4 alkyl ether group, substituted or unsubstituted C7 to C20 Arylalkylene ether group, substituted or unsubstituted C1 to C30 haloalkyl group, substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,
, R'및 R' '는 각각 독립적으로 치환 또는 비치환된 방향족 고리 함유기이되, R, R'또는 R" 는 치환 또는 비치환된 아민기, 치환 또는 비치환된 비닐기, 치환 또는 비치환된 아세틸렌기 , 아자이드기， 또는 나이트릴기를 적어도 하나 포함한다. 예를 들어, R, R'또는 R" 는 예컨대 1개 또는 2개의 치환 또는 비치환된 아민기, 치환 또는 비치환된 비닐기, 치환 또는 비치환된 아세틸렌기， 아자이드기, 또는 나이트릴기 치환된 것일 수 있다. , R 'and R' 'are each independently a substituted or unsubstituted aromatic ring containing group, R, R' or R "is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted At least one of an acetylene group, an azide group, or a nitrile group. For example, R, R ′, or R ″ may be, for example, one or two substituted or unsubstituted amine groups, a substituted or unsubstituted vinyl group. , Substituted or unsubstituted acetylene group, azide group, or nitrile group may be substituted.
상기 화학식 3으로 표현되는 첨가제는 상기 X로 표현되는 코어에 2개 또는 3개의 방향족 고리 함유기가 연결된 구조를 가진다. 상기 화학식 3으로 표현되는 첨가제가 3개의 치환기를 가지는 경우 상기 코어는 탄소 또는 질소이고 2개의 치환기를 가지는 경우 상기 코어는 직접결합, 탄소, 산소, 황, 또는 -S(02)-이다. 예를 들어, 상기 첨가제가 코어에 3개의 방향족 고리 함유기가 연결된 구조를 가질 경우 하기 화학식 4로 표현될 수 있고, 상기 첨가제가 코어에 2개의 방향족 고리 함유기가 연결된 구조를 가질 경우 하기 화학식 3로 표현될 수 있다. The additive represented by Chemical Formula 3 has a structure in which two or three aromatic ring-containing groups are connected to the core represented by X. When the additive represented by Formula 3 has three substituents, the core is carbon or nitrogen, and when the additive has two substituents, the core is a direct bond, carbon, oxygen, sulfur, or -S (0 2 )-. For example, when the additive has a structure in which three aromatic ring-containing groups are connected to the core, it may be represented by the following Formula 4, and when the additive has a structure in which two aromatic ring-containing groups are connected to the core, it is represented by the following Formula 3 Can be.
[화학식 4 [Formula 4
[화학식 5] [Formula 5]
R4— X— R5 R 4 — X— R 5
상기 화학식 4 및 5에서, In Chemical Formulas 4 and 5,
X1는— CH- 또는 질소 (N)이고, X 1 is — CH- or nitrogen (N),
X2는 직접결합, -(CqH2q)-, -(CtRw 2t)-, 산소 (0), 황 (S), -NH- 또는 -S(02)-이고, 여기서 q 및 t는 각각 독립적으로 1 내지 5인 정수이고 ^는 치환 또는 비치환된 C1 내지 C20 알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C1 내지 C20 알킬아민기, 치환 또는 비치환된 C7 내지 C20 아릴알킬기, 치환 또는 비치환된
CI 내지 C20 해테로알킬기, 치환 또는 비치환된 C2 내지 C30 X 2 is a direct bond,-(C q H 2 q)-,-(C t R w 2t )-, oxygen (0), sulfur (S), -NH- or -S (0 2 )-, wherein q and t are each independently integers of 1 to 5 and ^ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or Unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted CI to C20 heteroalkyl group, substituted or unsubstituted C2 to C30
헤테로사이클로알킬기， 치환 또는 비치환된 C2 내지 C30 헤테로아릴기， 치환 또는 비치환된 C1 내지 C4 알킬 에테르기, 치환 또는 비치환된 C7 내지 C20 아릴알킬렌 에테르기, 치환 또는 비치환된 C1 내지 C30 할로알킬기, 치환 또는 비치환된 C2 내지 C20 알케닐기 , 또는 이들의 조합이고, Heterocycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C1 to C4 alkyl ether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C1 to C30 Haloalkyl group, substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,
R1 내지 R5는 각각 독립적으로 그 구조 내에 하기 화학식 6으로 표현되는 기를 적어도 하나 포함하는 방향족 고리 함유기이다: R 1 to R 5 are each independently an aromatic ring containing group containing at least one group represented by the following formula (6) in its structure:
[화학식 6] [Formula 6]
(W)a (W) a
상기 화학식 6에서, In Chemical Formula 6,
W는 0, S, NRa또는 CRbRc이고， 여기서 Ra 내지 ^는 각각 독립적으로 수소 치환 또는 비치환된 C1 내지 C 10 알킬기， 할로겐 원자, 할로겐 함유기 또는 이들의 조합이고, W is 0, S, NR a or CR b R c , wherein R a to ^ are each independently a hydrogen substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group or a combination thereof,
Y는 치환 또는 비치환된 아민기, 치환 또는 비치환된 비닐기， 치환 또는 비치환된 아세틸렌기, 아자이드기, 나이트릴기, 또는 이들의 조합이고， Y is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, a nitrile group, or a combination thereof,
a는 0 또는 1이고, a is 0 or 1,
b는 0 내지 10의 정수이고, b is an integer from 0 to 10,
*는 연결지점이다. * Is the connection point.
예를 들어, 상기 화학식 4 및 5에서, R1 내지 R5는 각각 독립적으로 하기 화학식 7로 표현될 수 있으나, 이에 한정되는 것은 아니다.
[화학식 7] For example, in Formulas 4 and 5, R 1 to R 5 may be each independently represented by the following Formula 7, but are not limited thereto. [Formula 7]
Rla 내지 은 각각 독립적으로 수소, 히드록시기, 치환 또는 비치환된 C1 내지 C10 알킬기, 또는 상기 화학식 6으로 표시되는 기이되, Rla 내지 R13a 중 적어도 하나는 상기 화학식 6으로 표시되는 기이고, R la to are each independently hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, or a group represented by Formula 6, wherein at least one of R la to R 13a is a group represented by Formula 6,
T1 및 T2는 각각 독립적으로 0, S, NRa 또는 CRbRc이고, 여기서 Ra 내지 Rc는 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 할로겐 원자, 할로겐 함유기 또는 이들의 조합이고, T 1 and T 2 are each independently 0, S, NR a or CR b R c , wherein R a to R c are each independently hydrogen, a substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group Or a combination thereof,
c 및 d는 각각 독립적으로 0 내지 5인 정수이고, c and d are each independently an integer of 0 to 5,
*는 연결지점이다. * Is the connection point.
예를 들어， 상기 첨가제는 하기 화학식 Y1 내지 Y4 중 어느 하나로 표현될 수 있으나, 이에 한정되는 것은 아니다. For example, the additive may be represented by any one of the following Formulas Y1 to Y4, but is not limited thereto.
[화학식 Y1] [Formula Y1]
[화학식 Formula
상기 화학식 Y1 내지 Y4에서， In Chemical Formulas Y1 to Y4,
Τ3 및 Τ4는 각각 독립적으로 0, S, NRa 또는 CRbRc이고, 여기서 Ra 내지 Rc는 각각 독립적으로 수소, 치환 또는 비치환된 C 1 내지 C10 알킬기, 할로겐 원자, 할로겐 함유기 또는 이들의 조합이고, Τ 3 and Τ 4 are each independently 0, S, NR a or CR b R c , wherein R a to R c are each independently hydrogen, a substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing Groups or a combination thereof,
Rx 내지 Ry는 각각 독립적으로 수소， 할로겐 원자, 할로겐 함유기, 또는 치환 또는 비치환된 C1 내지 C20 알킬기이고, R x to R y are each independently hydrogen, a halogen atom, a halogen-containing group, or a substituted or unsubstituted C1 to C20 alkyl group,
R33 내지 R55은 각각 독립적으로 상기 화학식 6으로 표시되는 기이다ᅳ 예를 들어, 상기 첨가제는 그 구조 내에 적어도 하나의 산소 원자, 또는 질소 원자를 포함할 수 있으며， 예컨대 1개 내지 3개의 산소원자, 또는 1개의 질소원자를 포함할 수 있으나 이에 한정되는 것은 아니다. R 33 to R 55 are each independently a group represented by Formula 6 above. For example, the additive may include at least one oxygen atom or nitrogen atom in the structure thereof, for example, 1 to 3 oxygen atoms. It may include, but is not limited to, an atom or one nitrogen atom.
상기 첨가제는 예컨대 가교제와 같은 작용을 할 수 있다 The additive can act, for example, as a crosslinking agent.
이와 같이 상기 유기막 조성물은 아세틸렌이 도입된 중합체, 그리고 방향족 고리 함유 화합물로서 치환 또는 비치환된 아민기, 치환 또는 비치환된 비닐기, 치환 또는 비치환된 아세틸렌기, 아자이드기, 또는 나이트릴기를 적어도 하나 포함하는 첨가제를 포함한다. As described above, the organic film composition may include a polymer having acetylene introduced therein, and an substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, or nitrile as an aromatic ring-containing compound. Additives comprising at least one group.
이와 같이 상기 중합체 및 첨가제를 동시에 사용하는 경우， 상기 중합체에 도입된 아세틸렌 작용기가 경화 시 상기 첨가제에 도입된 아민， 아세틸렌, 아자이드 등과 반웅하여 고리가 형성됨에 따라 탄소 함량이 상대적으로 증가하게 된다ᅳ 이에 따라 내식각성이 향상되어 에치 선택비도 향상될 수 있다. 따라서, 상기 유기막 조성물을 사용하여 형성된 유기막은 막 밀도 및 패턴 형성성이 우수하다. As such, when the polymer and the additive are used at the same time, the carbon content is relatively increased as the acetylene functional group introduced into the polymer reacts with the amine, acetylene, and azide introduced into the additive during curing to form a ring. Accordingly, the etching resistance may be improved, and the etch selectivity may be improved. Therefore, the organic film formed using the organic film composition is excellent in film density and pattern formability.
예를 들어, 상기 중합체는 약 500 내지 200,000의 중량평균분자량을 가질 수 있다. 상기 범위의 중량평균분자량을 가짐으로써 상기 중합체를 포함하는 유기막 조성물 (예컨대, 하드마스크 조성물)의 탄소 함량 및 용매에 대한
용해도를 조절하여 최적화할 수 있다. 또한 예를 들어， 상기 첨가제는 약 150 내지 50,000의 분자량을 가질 수 있다. For example, the polymer may have a weight average molecular weight of about 500 to 200,000. By having a weight average molecular weight in the above range for the carbon content and the solvent of the organic film composition (eg, hard mask composition) comprising the polymer Solubility can be adjusted to optimize. Also for example, the additive may have a molecular weight of about 150 to 50,000.
상기 유기막 조성물에 포함되는 용매는 상기 중합체에 대한 층분한 용해성 또는 분산성을 가지는 것이면 특별히 한정되지 않으나, 예컨대 프로필렌글리콜, 프로필렌글리콜 디아세테이트, 메특시 프로판디올, 디에틸렌글리콜, The solvent included in the organic film composition is not particularly limited as long as it has a good solubility or dispersibility in the polymer, for example, propylene glycol, propylene glycol diacetate, mesopropanediol, diethylene glycol,
디에틸렌글리콜 부틸에테르, 트리 (에틸렌글리콜)모노메틸에테르, 프로필렌글리콜 모노메틸에테르, 프로필렌글리콜 모노메틸에테르 아세테이트, 사이클로핵사논, 에틸락테이트, 감마-부티로락톤, Ν,Ν-디메틸포름아미드, Ν,Ν-디메틸아세트아미드, 메틸피를리돈, 메틸피를리디논, 아세틸아세톤 및 에틸 3- 에록시프로피오네이트에서 선택되는 적어도 하나를 포함할 수 있다. Diethylene glycol butyl ether, tri (ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclonucleanone, ethyl lactate, gamma-butyrolactone, Ν, Ν-dimethylformamide, And at least one selected from Ν, Ν-dimethylacetamide, methylpyridone, methylpyridinone, acetylacetone and ethyl 3-ethoxypropionate.
상기 중합체는 상기 유기막 조성물의 총 함량에 대하여 약 0.1 내지 50 중량 %로 포함될 수 있다. 상기 범위로 중합체가 포함됨으로써 유기막의 두께, 표면 거칠기 및 평탄화 정도를 조절할 수 있다. The polymer may be included in about 0.1 to 50% by weight based on the total content of the organic film composition. By including the polymer in the above range it is possible to control the thickness, surface roughness and degree of planarization of the organic film.
상기 첨가제는 상기 유기막 조성물의 총 함량에 대하여 약 0.1 내지 50 중량 %로 포함될 수 있고, 예컨대 상기 유기막 조성물의 총 함량에 대하여 약 5 내지 50 중량0 /。로 포함될 수 있다. 상기 범위로 첨가제가 포함됨으로써 제조되는 유기막의 초기 평탄화도를 향상시킬 수 있다. The additive may be included in about 0.1 to 50% by weight based on the total content of the organic film composition, for example, may be included in about 5 to 50% by weight 0 /. By including the additive in the above range it is possible to improve the initial planarization of the organic film produced.
상기 유기막 조성물은 추가적으로 계면활성게, 가교제, 열산 발생제, 가소제 등의 첨가제를 더 포함할 수 있다. The organic film composition may further include additives such as a surfactant, a crosslinking agent, a thermal acid generator, and a plasticizer.
상기 계면활성제는 예컨대 알킬벤젠설폰산 염, 알킬피리디늄 염, 폴리에틸렌글리콜, 제 4 암모늄 염 등을 사용할 수 있으나 이에 한정되는 것은 아니다. The surfactant may be, for example, alkylbenzenesulfonic acid salt, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt and the like, but is not limited thereto.
상기 가교제는 예컨대 멜라민계, 치환요소계, 또는 이들 폴리머계 등을 들 수 있다ᅳ 바람직하게는, 적어도 2개의 가교형성 치환기를 갖는 가교제로， 예를 들면, 메록시메틸화 글리코루릴, 부록시메틸화 글리코루릴, 메톡시메틸화 멜라민, 부톡시메틸화 멜라민, 메록시메틸화 벤조구아나민, 부록시메틸화 벤조구아나민, 메톡시메틸화요소, 부록시메틸화요소, 메특시메틸화 티오요소, 또는 부록시메틸화 티오요소 등의 화합물을 사용할 수 있다. The crosslinking agent is, for example melamine type, a substituted urea, or a cross-linker having these can be given a polymer such as eu Preferably, at least two cross-link the substituent, for example, methoxy hydroxy methylated glycosides ruril, Appendix during methylation glycolate Such as ruryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, annexed methylated benzoguanamine, methoxymethylated urea, annexed methylated urea, methoxymethylated thiourea, or an appendoxymethylated thiourea Compounds can be used.
또한, 상기 가교제로는 내열성이 높은 가교제를 사용할 수 있다. 내열성이 높은 가교제로는 분자 내에 방향족환 (예를 들면 벤젠환, 나프탈렌환)을 가지는
가교형성 치환기를 함유하는 화합물을 사용할 수 있다. In addition, a crosslinking agent having high heat resistance may be used as the crosslinking agent. The crosslinking agent having high heat resistance has an aromatic ring (for example, a benzene ring or a naphthalene ring) in the molecule. Compounds containing crosslinking substituents can be used.
상기 열산발생제는 예컨대 P-를루엔술폰산, 트리플루오로메탄술폰산, 피리디늄 P-틀루엔술폰산, 살리실산, 술포살리실산, 구연산, 안식향산, The thermal acid generators include, for example, P-luenesulfonic acid, trifluoromethanesulfonic acid, pyridinium P-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid,
하이드록시안식향산, 나프탈렌카르본산 등의 산성 화합물 또는 /및 2，4,4,6- 테트라브로모시클로핵사디에논, 벤조인토실레이트, 2-니트로벤질토실레이트, 그 밖에 유기술폰산알킬에스테르 등을 사용할 수 있으나 이에 한정되는 것은 아니다. 상기 첨가제는 상기 유기막 조성물 100 중량부에 대하여 약 0.001 내지 40중량부로 포함될 수 있다. 상기 범위로 포함함으로써 유기막 조성물의 광학적 특성을 변경시키지 않으면서 용해도를 향상시킬 수 있다. Acidic compounds such as hydroxybenzoic acid, naphthalenecarboxylic acid, and / or 2,4,4,6-tetrabromocyclonuxadienone, benzointosylate, 2-nitrobenzyltosylate, and other alkyl esters It may be used, but is not limited thereto. The additive may be included in an amount of about 0.001 to 40 parts by weight based on 100 parts by weight of the organic film composition. By including in the said range, solubility can be improved without changing the optical characteristic of an organic film composition.
또 다른 구현예에 따르면， 상술한 유기막 조성물을 사용하여 제조된 유기막을 제공한다. 상기 유기막은 상술한 유기막 조성물을 예컨대 기판 위에 코팅한 후 열처리 과정을 통해 경화된 형태일 수 있으며， 예컨대 하드마스크 층, 평탄화 막, 희생막, 층진제, 등 전자 디바이스에 사용되는 유기 박막을 포함할 수 있다ᅳ According to another embodiment, an organic film prepared using the organic film composition described above is provided. The organic layer may be in the form of the above-described organic layer composition, for example, coated on a substrate and cured through a heat treatment process, and may include, for example, an organic thin film used in an electronic device such as a hard mask layer, a planarization layer, a sacrificial layer, a layer release agent, and the like. I can do it
이하 상술한 유기막 조성물을 사용하여 패턴을 형성하는 방법에 대하여 설명한다. Hereinafter, the method of forming a pattern using the organic film composition mentioned above is demonstrated.
일 구현예에 따른 패턴 형성 방법은 기판 위에 재료 층을 제공하는 단계, 상기 재료 층 위에 상술한 중합체 및 용매를 포함하는 유기막 조성물을 적용하는 단계, 상기 유기막 조성물을 열처리하여 하드마스크 층을 형성하는 단계, 상기 하드마스크 층 위에 실리콘 함유 박막층을 형성하는 단계, 상기 실리콘 함유 박막층 위에 포토레지스트 층을 형성하는 단계, 상기 포토레지스트 층을 노광 및 현상하여 포토레지스트 패턴을 형성하는 단계， 상기 포토레지스트 패턴을 According to one or more exemplary embodiments, a method of forming a pattern includes: providing a material layer on a substrate, applying an organic film composition including the polymer and a solvent on the material layer, and heat treating the organic film composition to form a hard mask layer. Forming a photoresist layer on the hard mask layer; exposing and developing the photoresist layer; forming a photoresist pattern by exposing and developing the photoresist layer; of
이용하여 상기 실리콘 함유 박막층 및 상기 하드마스크 층을 선택적으로 Using the silicon-containing thin film layer and the hard mask layer selectively
제거하고 상기 재료 층의 일부를 노출하는 단계， 그리고 상기 재료 층의 노출된 부분을 식각하는 단계를 포함한다. Removing and exposing a portion of the material layer, and etching the exposed portion of the material layer.
상기 기판은 예컨대 실리콘웨이퍼, 유리 기판 또는 고분자 기판일 수 있다. 상기 재료 층은 최종적으로 패턴하고자 하는 재료이며, 예컨대 알루미늄, 구리 등과 같은 금속층, 실리콘과 같은 반도체 층 또는 산화규소, 질화규소 등과 같은 절연층일 수 있다. 상기 재료 층은 예컨대 화학기상증착 방법으로 형성될 수 있다.
상기 유기막 조성물은 전술한 바와 같으며, 용액 형태로 제조되어 스핀-온 코팅 방법으로 도포될 수 있다. 이 때 상기 유기막 조성물의 도포 두께는 특별히 한정되지 않으나， 예컨대 약 50 내지 Ι Ο,ΟΟΟ Α 두께로 도포될 수 있다. 상기 유기막 조성물을 열처리하는 단계는 예컨대 약 100 내지 500 °C에서 약 10초 내지 1시간 동안 수행할 수 있다. 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, for example, a metal layer such as aluminum or copper, a semiconductor layer such as silicon, or an insulating layer such as silicon oxide, silicon nitride, or the like. The material layer can be formed, for example, by chemical vapor deposition. The organic film composition is as described above, it 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, and for example, may be applied to a thickness of about 50 to ΙΟΟΟΟΟΑΑ. The heat treatment of the organic layer composition may be performed, for example, at about 100 to 500 ° C for about 10 seconds to 1 hour.
예를 들어, 상기 열처리는 50 내지 250 °C에서 진행되는 게 1차 열처리, 그리고 상기 제 1 열처리에 후속되고 200 내지 500 °C에서 진행되는 제 2차 열처리를 포함할 수 있다. For example, the heat treatment may include a first heat treatment performed at 50 to 250 ° C, and a second heat treatment following the first heat treatment and proceeding at 200 to 500 ° C.
상기 실리콘 함유 박막층은 예컨대 SiCN, SiOC, SiON, SiOCN, SiC 및 /또는 SiN 등의 물질로 형성할 수 있다. The silicon-containing thin film layer may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, and / or SiN.
또한 상기 포토레지스트 층을 형성하는 단계 전에 상기 실리콘 함유 박막층 상부에 바닥 반사방지 층 (bottom anti-reflective coating, BARC)을 더 형성할 수도 있다. In addition, a bottom anti-reflective coating (BARC) may be further formed on the silicon-containing thin film layer before the forming of the photoresist layer.
상기 포토레지스트 층을 노광하는 단계는 예컨대 ArF, KrF 또는 EUV 등을 사용하여 수행할 수 있다. 또한 노광 후 약 100 내지 500 °C에서 열처리 공정을 수행할 수 있다. Exposing the photoresist layer may be performed using, for example, ArF, KrF or EUV. In addition, a heat treatment process may be performed at about 100 to 500 ° C after exposure.
상기 재료 층의 노출된 부분을 식각하는 단계는 식각 가스를 사용한 건식 식각으로 수행할 수 있으며, 식각 가스는 예컨대 CHF3, CF4, Cl2, BC13 및 이들의 흔합 가스를 사용할 수 있다. Etching the exposed portion of the material layer may be performed by dry etching using an etching gas, which may use, for example, CHF 3 , CF 4 , Cl 2 , BC1 3, and a combination thereof.
상기 식각된 재료 층은 복수의 패턴으로 형성될 수 있으며， 상기 복수의 패턴은 금속 패턴, 반도체 패턴, 절연 패턴 등 다양할 수 있으며， 예컨대 반도체 집적 회로 디바이스 내의 다양한 패턴으로 적용될 수 있다. 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, for example, various patterns in a semiconductor integrated circuit device.
【발명의 실시를 위한 형태】 [Form for implementation of invention]
이하 실시예를 통하여 상술한 본 발명의 구현예를 보다 상세하게 설명한다. 다만 하기의 실시예는 단지 설명의 목적을 위한 것이며 본 발명의 범위를 제한하는 것은 아니다. 중합체 합성 Through the following examples will be described in more detail the embodiment of the present invention. However, the following examples are merely for illustrative purposes and do not limit the scope of the present invention. Polymer synthesis
중합예 1
레진 중합 Polymerization Example 1 Resin polymerization
플라스크에 naphthalen-l-ol(14.2g), 파라포름알데하이드 (6g),p-를루엔 Naphthalen-l-ol (14.2 g), paraformaldehyde (6 g), p-luene in the flask
술폰산 수화물 (1.9 g) 및 프로필렌글리콜 모노메틸에테르아세테이트 (PGMEA) (33 g) 를 투입한 후, 80°C에 교반하여 중합 반웅을 수행하였다. 반웅을 진행되는 동안 Sulphonic acid hydrate (1.9 g) and propylene glycol monomethyl ether acetate (PGMEA) (33 g) were added, followed by stirring at 80 ° C. to carry out polymerization reaction. During the reaction
GPC로 분자량을 확인하여 중량평균분자량이 2,000 내지 3,500일 때 반응을 완료하였다. 중합 반웅이 완료된 후, 반웅물을 상온으로 서서히 넁각시킨 후 핵산 100g을 넣어 프로필렌글리콜 모노메틸에테르아세테이트 추출해 낸 후 증류수 및 메탄올을 이용하여 제거하여 하기 화학식 la'로 표현되는 구조단위를 포함하는 중합체를 얻었다 (중량평균분자량 (Mw)= 3,000). The molecular weight was confirmed by GPC to complete the reaction when the weight average molecular weight was 2,000 to 3,500. After the completion of the polymerization reaction, the reaction product was slowly cooled down to room temperature, 100 g of nucleic acid was added thereto to extract propylene glycol monomethyl ether acetate, and then removed using distilled water and methanol to remove the polymer including the structural unit represented by the following formula la '. (Weight average molecular weight (Mw) = 3,000).
la'] la ']
아세틸화 (AcetylationJ 반웅 Acetylation (AcetylationJ reaction)
플라스크에 화학식 la'의 구조단위를 포함하는 중합체 (10 g)을 DMF(40 mL)에 녹인 후 얼음물에서 교반한다. 교반 10분 후 NaH(l g)을 천천히 적가한 후 얼음물에서 30분간 교반한 후 프로파질브로마이드(80%^101 ^6)(5.5^를 In a flask, a polymer (10 g) containing a structural unit of formula la 'is dissolved in DMF (40 mL) and stirred in ice water. After 10 minutes of stirring, NaH (l g) was slowly added dropwise and stirred in ice water for 30 minutes, followed by propazyl bromide (80% ^ 101 ^ 6) (5.5 ^
적가한다. 반웅이 완결되면 EtOAc(lOOmL) 을 넣에 반웅액올 희석 시킨 후 물로 여러 번 씻어서 DMF를 제거해 준다. DMF가 완전히 제거 되면 남아있는 EtOAc를 제거하여 중합체 la를 얻었다. 중합예 2 Add it down. When the reaction was completed, dilute the reaction solution in EtOAc (100 mL) and wash it several times with water to remove DMF. When DMF was completely removed, the remaining EtOAc was removed to give polymer la. Polymerization Example 2
레진 중합 Resin polymerization
naphthalen-1-ol (10 g), l,3-bis(4-(methoxymethyl)phenoxy)benzene (24.3 g), naphthalen-1-ol (10 g), l, 3-bis (4- (methoxymethyl) phenoxy) benzene (24.3 g),
프로필렌글리콜 모노메틸에테르아세테이트 (PGMEA)(64g) 및 Propylene glycol monomethyl ether acetate (PGMEA) (64 g) and
디에틸설페이트( 1^1^ 1 (0.3 을 100°C에서 합성예 1의 레진 중합과 같은 방법을 이용하여 화학식 lb'로 표현되는 구조단위를 포함하는 중합체를 얻었다. (중량평균분자량 (Mw)= 3,500).
Diethyl sulfate (1 ^ 1 ^ 1 (0.3 at 100 ° C.) was used to obtain a polymer containing the structural unit represented by the formula lb 'using the same method as the resin polymerization of Synthesis Example 1. (Weight average molecular weight (Mw) = 3,500).
아세틸화 (AcetylationJ 반웅 Acetylation (AcetylationJ reaction)
화학식 lb' 의 구조단위를 포함하는 중합체 (10 g), DMF (50 mL), NaH (0.6 g), 및 프로파질브로마이드 (80% in tolutene)(2.6 g)을 이용하여 합성예 1의 동일한 방법으로 아세틸화 하여 중합체 lb를 얻었다. 중합예 3 The same method as in Synthesis Example 1 using a polymer comprising a structural unit of formula lb '(10 g), DMF (50 mL), NaH (0.6 g), and propazylbromide (80% in tolutene) (2.6 g) Acetylation was carried out to obtain the polymer lb. Polymerization Example 3
레진 중합 Resin polymerization
pyrene-l ,6-diol(23g), l ,4-bis(methoxymethyl)benzene(25g), 프로필렌글리콜 모노메틸에테르아세테이트 (PGMEA) (48g) 및 디에틸설페이트 (diethylsulfate) (0.7g)를 투입하고 100 °C에서 교반하여 중합 반웅을 수행하였다. 중량평균분자량이 2,000 내지 3,500일 때 반웅을 완료하였다. 중합 반웅이 완료된 후， 반웅물을 상온으로 서서히 냉각시킨 후 상기 반웅물을 증류수 20g 및 메탄올 200g에 투입하여 강하게 교반한 후, 정치시켰다. 상등액을 제거하고 침전물을 프로필렌글리콜 모노메틸에테르아세테이트 (PGMEA) 40g에 녹인 후, 메탄올 160g, 물 160g를 이용하여 강하게 교반한 후, 정치시켰다 0차). 이때 얻어지는 상등액을 다시 제거하고 침전물을 프로필렌글리콜 모노메틸에테르아세테이트 (PGMEA) 40g에 녹였다 (2차). 상기 1차 및 2차 공정을 1회 정제 공정이라 하고, 이 정제 공정을 총 3회 실시하였다. 정제가 끝난 중합체를 프로필렌글리콜 pyrene-l, 6-diol (23g), l, 4-bis (methoxymethyl) benzene (25g), propylene glycol monomethyl ether acetate (PGMEA) (48g) and diethylsulfate (0.7g) The polymerization reaction was carried out by stirring at 100 ° C. The reaction was completed when the weight average molecular weight was 2,000 to 3,500. After the polymerization reaction was completed, the reaction product was slowly cooled to room temperature, and then the reaction product was added to 20 g of distilled water and 200 g of methanol, and the mixture was stirred strongly. The supernatant was removed and the precipitate was dissolved in 40 g of propylene glycol monomethyl ether acetate (PGMEA), followed by vigorous stirring using 160 g of methanol and 160 g of water, followed by standing still. The supernatant obtained at this time was removed again and the precipitate was dissolved in 40 g of propylene glycol monomethyl ether acetate (PGMEA) (secondary). The first and second processes were referred to as one-time purification processes, and this purification process was performed three times in total. Purified polymer propylene glycol
모노메틸에테르아세테이트 (PGMEA) 40g에 녹인 후, 감압 하에서 용액에 남아있는 메탄을 및 증류수를 제거하여 화학식 1C로 표현되는 구조단위를 포함하는 중합체를 얻었다. (중량평균분자량 (Mw)= 2,600).
lc'] After dissolving in 40 g of monomethyl ether acetate (PGMEA), methane remaining in the solution and distilled water were removed under reduced pressure to obtain a polymer including a structural unit represented by Chemical Formula 1C. (Weight average molecular weight (Mw) = 2,600). lc ']
아세틸화 (AcetylationJ 반웅 Acetylation (AcetylationJ reaction)
화학식 lc' 의 구조단위를 포함하는 증합체 (10g),DMF(40mL),NaH(0.6g) 및 프로파질브로마이드 (80%intolutene)(2.2g)을 이용하여 합성예 1의 동일한 방법으로 아세틸화 하여 중합체 lc를 얻었다. 중합예 4 Acetylation in the same manner as in Synthesis Example 1 using a multimer (10 g), DMF (40 mL), NaH (0.6 g) and propazyl bromide (80% intolutene) (2.2 g) comprising the structural unit of formula lc ' To give the polymer lc. Polymerization Example 4
레진 중합 ᅳ Resin polymerization ᅳ
4,4'-(9H-플루오렌 -9,9-디일)디페놀 (4,4'-(9H-fluorene-9,9-diyl)cUphenol) (14 g), 4,4 '-(9H-fluorene-9,9-diyl) diphenol (4,4'-(9H-fluorene-9,9-diyl) cUphenol) (14 g),
1,4-비스 (메특시메틸)벤젠 (l,3-bis(methoxymethyl)benzene) (6.6 g), 프로필렌글리콜 모노메틸에테르아세테이트 (PGMEA) (20 g) 및 디에틸설페이트 (diethylsulfate) (0.25 g)를 100°C에서 합성예 1의 레진 중합과 같은 방법을 이용하여 화학식 Id'로 표현되는 구조단위를 포함하는 중합체를 얻었다. (중량평균분자량 (Mw)= 3,700). 1,4-bis (methoxymethyl) benzene (6.6 g), propylene glycol monomethyl ether acetate (PGMEA) (20 g) and diethylsulfate (0.25 g ) At 100 ° C using a method similar to the resin polymerization of Synthesis Example 1 to obtain a polymer containing a structural unit represented by the formula (Id '). (Weight average molecular weight (Mw) = 3,700).
[화학식 Id'] Formula Id '
아세틸화 (AcetylationJ 반웅 Acetylation (AcetylationJ reaction)
화학식 id' 의 구조단위를 포함하는 중합체 (9 g), DMF (45 mL), NaH (0·9 g), 및 프로파질브로마이드(80%^1101 ∞6)(3.5^올 이용하여 합성예 1의 동일한 방법으로 아세틸화 하여 중합체 Id를 얻었다. 중합예 5
레진 중합 Polymer (9 g), DMF (4 5 mL) containing a structure unit represented by the formula id ', NaH (0 · 9 g), and propargyl bromide (80% ^ 1101 ∞6) ( 3.5 ^ ol Synthesis Example using Acetylation was carried out in the same manner as 1. Polymer Id was obtained. Resin polymerization
6,6'-(9H-fluorene-9,9-diyl)dinaphthalen-2-ol (18 g), 1,3-비스 (메록시메틸)벤젠 (1,3- bis(methoxymethyl)benzene) (6.6 g), 프로필렌글리콜 6,6 '-(9H-fluorene-9,9-diyl) dinaphthalen-2-ol (18 g), 1,3-bis (methoxymethyl) benzene (1,3-bis (methoxymethyl) benzene) (6.6 g), propylene glycol
모노메틸에테르아세테이트 (PGMEA) (25 g) 및 디에틸설페이트 (diethylsulfate) (0.2 g)를 110°C에서 합성예 1의 레진 중합과 같은 방법을 이용하여 화학식 le'로 표현되는 구조단위를 포함하는 중합체를 얻었다ᅳ (중량평균분자량 (Mw)= 3,800). Monomethyl ether acetate (PGMEA) (25 g) and diethylsulfate (0.2 g) containing a structural unit represented by the formula le 'at 110 ° C using the same method as the resin polymerization of Synthesis Example 1 A polymer was obtained (weight average molecular weight (Mw) = 3,800).
le'] le ']
아세틸화 (AcetylationJ 반웅 Acetylation (AcetylationJ reaction)
화학식 le'의 구조단위를 포함하는 중합체 (10g), DMF(45mL),NaH(0.7g) 및 프로파질브로마이드(80%^101 6^)(2.5 을 이용하여 합성예 1의 동일한 방법으로 아세틸화 하여 중합체 le를 얻었다. 중합예 6 Acetylation in the same manner as in Synthesis Example 1 using polymer (10 g), DMF (45 mL), NaH (0.7 g) and propazyl bromide (80% ^ 101 6 ^) (2.5) To obtain polymer le Polymerization Example 6
4,4'-(9H-fluorene-9,9-diyl)dibenzene- 1 ,2-dioll (38 g), 5 -hydroxy- 1 -naphthaldehyde 4,4 '-(9H-fluorene-9,9-diyl) dibenzene-1,2-dioll (38 g), 5 -hydroxy-1 -naphthaldehyde
(17 g) 프로필렌글리콜 모노메틸에테르아세테이트 (PGMEA) (129 g) 및 (17 g) propylene glycol monomethyl ether acetate (PGMEA) (129 g) and
디에틸설페이트 (diethylsulfate) (으3 g)을 사용하여 100°C에서 합성예 1의 레진 중합과 같은 방법을 이용하여 화학식 If로 표현되는 구조단위를 포함하는 중합체를 얻었다 .(Mw: 3,200).Using diethylsulfate (3 g) to obtain a polymer containing a structural unit represented by the formula If using the same method as the resin polymerization of Synthesis Example 1 at 100 ° C. (Mw: 3,200).
화학식 If] Formula If]
아세틸화 (Acetylation_) 반웅 Acetylation
화학식 if의 구조단위를 포함하는 중합체 (10g),DMF(50mL),NaH(1.9g)
및 프로파질브로마이드(80%^ 1 ^6)(5.1 을 이용하여 합성예 1의 동일한 방법으로 아세틸화 하여 중합체 If를 얻었다. 중합예 7 Polymer containing structural unit of formula if (10 g), DMF (50 mL), NaH (1.9 g) And acetylation in the same manner as in Synthesis Example 1 using propazyl bromide (80% ^ 1 ^ 6) (5.1).
레진 중합 Resin polymerization
5,5'-(9H-fluorene-9,9-diyl)dibenzene-l,2,3-triol (20 g), 4,4'- oxybis((methoxymethyl)benzene) (26 g), IH-indol (6 g), 프로필렌글리콜 5,5 '-(9H-fluorene-9,9-diyl) dibenzene-l, 2,3-triol (20 g), 4,4'-oxybis ((methoxymethyl) benzene) (26 g), IH-indol (6 g), propylene glycol
모노메틸에테르아세테이트 (PGMEA) (123 g) 및 디에틸설페이트 (diethylsulfate) (0.5 g)을 사용하여 10( C에서 합성예 1과 동일한 합성과정을 거쳐 화학식 lg'로 표현되는 구조단위를 포함하는 중합체를 얻었다 (Mw: 3,300). A polymer comprising a structural unit represented by the formula lg 'through 10 (C same synthesis as in Synthesis Example 1) using monomethyl ether acetate (PGMEA) (123 g) and diethylsulfate (0.5 g). (Mw: 3,300).
lg': lg ':
아세틸화 (AcetylationJ 반웅 Acetylation (AcetylationJ reaction)
화학식 lg'의 구조단위를 포함하는 중합체 (10g),DMF(50mL),NaH(1.3g) 및 프로파질브로마이드 (80%intolutene)(3.7g)을 이용하여 합성예 1의 동일한 방법으로 아세틸화 하여 중합체 lg를 얻었다. 중합예 8 Acetylation was carried out in the same manner as in Synthesis Example 1 using polymer (10 g), DMF (50 mL), NaH (1.3 g), and propazyl bromide (80% intolutene) (3.7 g) containing the structural unit of formula lg '. Polymer lg was obtained. Polymerization Example 8
레진 중합 Resin polymerization
naphthalen-1-ol (7.2 g), IH-indol (5.9 g), 4-hydroxy- 1 -naphthaldehyde (17g) 프로필렌글리콜 모노메틸에테르아세테이트 (PGMEA)(129g) 및 naphthalen-1-ol (7.2 g), IH-indol (5.9 g), 4-hydroxy-1 -naphthaldehyde (17 g) propylene glycol monomethyl ether acetate (PGMEA) (129 g) and
디에틸설페이트 (diethylsulfate) (0.3 g)을 사용하여 합성예 1과 동일한 합성과정을 거쳐 화학식 ih'로 표현되는 구조단위를 포함하는 중합체를 얻었다 (Mw: 3,700).
Diethylsulfate (0.3 g) was used to obtain a polymer including the structural unit represented by Formula ih 'through the same synthesis procedure as in Synthesis Example 1 (Mw: 3,700).
아세틸화 (AcetylationJ 반웅 Acetylation (AcetylationJ reaction)
화학식 lh' 의 구조단위를 포함하는 중합체 (12g), DMF(55mL),NaH(l g) 및 프로파질브로마이드 (80%intolutene)(3.4g)을 이용하여 합성예 1의 동일한 방법으로 아세틸화 하여 중합체 lh를 얻었다. 중합예 9 Polymer obtained by acetylating in the same manner as in Synthesis Example 1 using polymer (12 g), DMF (55 mL), NaH (lg) and propazyl bromide (80% intolutene) (3.4 g) containing the structural unit of formula lh ' got lh. Polymerization Example 9
레진 중합 Resin polymerization
플라스크에 카바졸 (16g),5-hydroxy-l-naphthaldehyde(17g), P-를루엔 술폰산 수화물 (p-Toluenesulfonicacidmonohydrate)(1.9g), 1,4-다이옥산 (32 g)을 첨가한 후 To the flask was added carbazole (16 g), 5-hydroxy-l-naphthaldehyde (17 g), p-toluenesulfonicacidmonohydrate (1.9 g), 1,4-dioxane (32 g)
100 °C에서 교반하였다. 이에 따라 얻어진 중합 반응물로부터 1시간 간격으로 시료를 취하여， 그 시료의 중량평균 분자량이 2000 내지 3000 때 반웅을 Stir at 100 ° C. The samples are taken from the polymerization reaction product obtained in this manner at 1 hour intervals and reacted when the weight average molecular weight of the sample is 2000 to 3000.
완료하였다. 반웅이 완결되면 핵산 100g을 넣어 1,4-다이옥산을 추출해 낸 후 메탄올을 첨가하여 형성된 침전을 여과하고 남아있는 단량체를 메탄을을 이용하여 제거하여 하기 화학식 Π'로 표현되는 중합체를 얻었다 Completed. When the reaction was completed, 100 g of nucleic acid was added to extract 1,4-dioxane, and then, methanol was added to filter the precipitate formed, and the remaining monomers were removed using methane to obtain a polymer represented by the following Chemical Formula II.
(중량평균분자량 (Mw)= 2,600). (Weight average molecular weight (Mw) = 2,600).
아세틸화 (AcetylationJ 반웅 Acetylation (AcetylationJ reaction)
화학식 Π' 의 구조단위를 포함하는 중합체 (10g),DMF(55mL),NaH(0.65g) 및 프로파질브로마이드 (80%intolutene)(1.7g)을 이용하여 합성예 1의 동일한 방법으로 아세틸화 하여 중합체 Π를 얻었다.
중합예 10 Acetylation was carried out in the same manner as in Synthesis Example 1 using polymer (10 g), DMF (55 mL), NaH (0.65 g) and propazyl bromide (80% intolutene) (1.7 g) containing the structural unit of formula Polymer II was obtained. Polymerization Example 10
플라스크에 lH-indol-5-ol(13g), 9-플루오렌 (9-Fluorenone) (18 g), p-를루엔 술폰산 수화물 (p-Toluenesulfonicacidmonohydrate)(9.5 g), 1，4-다이옥산 (91 g)을 사용하여 합성예 9와 동일한 합성과정을 거쳐 화학식 lj'로 표현되는 구조단위를 포함하는 중합체를 얻었다 (Mw: 2,900). LH-indol-5-ol ( 13g) to the flask, 9-fluorenylmethoxycarbonyl (9-Fluorenone) (18 g ), p- toluene sulfonic acid monohydrate for (p-Toluenesulfonicacidmonohydrate) (9 5 g.), 1, 4 - dioxane Using (91 g), a polymer including a structural unit represented by formula lj 'was obtained through the same synthesis procedure as in Synthesis Example 9 (Mw: 2,900).
lj'] lj ']
아세틸화 (AcetylationJ 반웅 Acetylation (AcetylationJ reaction)
화학식 lj'의 구조단위를 포함하는 중합체 (10g), DMF(50mL),NaH(0.7g) 및 프로파질브로마이드(80%^101 6^)(1.8^을 이용하여 합성예 1의 동일한 방법으로 아세틸화 하여 중합체 lj를 얻었다ᅳ 비교 중합예 1 Acetyl Acetate in the same manner as in Synthesis Example 1 using polymer (10 g), DMF (50 mL), NaH (0.7 g) and propazyl bromide (80% ^ 101 6 ^) (1.8 ^) To obtain a polymer lj Comparative Polymerization Example 1
naphthalen-1-ol (14 g), 1 ,4-bis(methoxymethyl)benzene( 17g), 프로필렌글리콜 모노메틸에테르아세테이트 (PGMEA) (64 g) 및 디에틸설페이트 (diethylsulfate) (0.3 g) 을 io(rc에서 합성예 1의 레진 중합과 같은 방법을 이용하여 화학식 lk로 표현되는 구조단위를 포함하는 중합체 (중합체 lk)를 얻었다. naphthalen-1-ol (14 g), 1,4-bis (methoxymethyl) benzene (17g), propylene glycol monomethyl ether acetate (PGMEA) (64 g) and diethylsulfate (0.3 g) The polymer (polymer lk) containing the structural unit represented by general formula lk was obtained using the method similar to the resin polymerization of the synthesis example 1 in rc.
(중량평균분자량 (Mw)= 3,000). (Weight average molecular weight (Mw) = 3,000).
첨가제 합성 Additive synthesis
합성예 1
500ml 등근 플라스크에 stir bar, 4,4'-(4,4'-(propane-2,2-diyl)bis(4,l - phenylene))bis(oxy)dianiline (10 g), 물 (60 ml), crushed 얼음 (15 g)을 넣은 후 얼음물에서 10분간 교반한 후 cone. HC1 (20 ml)를 천천히 적가한다. 여기에 물 (15 ml)에 녹여놓은 NaN02를 dropping funnel올 이용하여 약 10분 동안 적가한다. 20분 교반 후 물 (15 ml)에 녹여놓은 KI를 dropping funnel을 이용하여 천천히 적가한다. 1시간 30분 교반 후 TLC를 확인하여 반응이 완결되면 필터하여 얻은 고체를 EA에 녹인후 NaHS03과 물을 이용하여 씻어준다. 유기층의 용매를 제거하여 하기 화학식 2a로 표현되는 첨가제 8g올 얻었다. Synthesis Example 1 In a 500 ml round flask, stir bar, 4,4 '-(4,4'-(propane-2,2-diyl) bis (4, l-phenylene)) bis (oxy) dianiline (10 g), water (60 ml ), add crushed ice (15 g) and stir in iced water for 10 minutes and then cone. HC1 (20 ml) is slowly added dropwise. Add NaN02 dissolved in water (15 ml) dropwise for about 10 minutes using a dropping funnel. After stirring for 20 minutes, KI dissolved in water (15 ml) is slowly added dropwise using a dropping funnel. After stirring for 1 hour and 30 minutes, the reaction was completed by checking the TLC. The solid obtained by filtering was dissolved in EA and washed with NaHS03 and water. The solvent of the organic layer was removed to obtain 8 g of an additive represented by the following Chemical Formula 2a.
[화학식 2a
합성예 2 [Formula 2a Synthesis Example 2
4,4'-(biphenyl-4,4'-diylbis(oxy))dianiline (9 g), NaN02 (4 g), NaN3 (4.7 g), cone. HCl (15 ml) 을 사용하여 합성예 1과 동일한 방법을 이용하여 하기 화학식 2b로 표현되는 첨가제를 얻었다. 4,4 '-(biphenyl-4,4'-diylbis (oxy)) dianiline (9 g), NaN02 (4 g), NaN3 (4.7 g), cone. Using HCl (15 ml) using the same method as in Synthesis Example 1 to obtain an additive represented by the following formula (2b).
2b] 2b]
4,4'-(biphenyl-4,4'-diylbis(oxy))dianiline (9 g), NaN02 (4 g), NaN3 (4.7 g), cone. HCl 4,4 '-(biphenyl-4,4'-diylbis (oxy)) dianiline (9 g), NaN02 (4 g), NaN3 (4.7 g), cone. HCl
(15 ml)을 사용하여 합성예 1과 동일한 방법을 이용하여 하기 화학식 2c로 표현되는 첨가제를 얻었다. -
(15 ml) was used to obtain an additive represented by the following Chemical Formula 2c using the same method as in Synthesis Example 1. -
4,4'-(4,4'-(propane-2,2-diyl)bis(4,l-phenylene))bis(oxy)dianiline (10 g), NaN02 (4 g), KI(12.1 g), cone. HC1 (20 ml) 을 사용하여 합성예 1과 동일한 방법을 이용하여 고체 중간체 (7.7g)을 얻었다. 얻어진 중간체 (5.7 g)을 테드라 하이드로 퓨란 (40mL)에 녹인 후, -40°C에서 pro-MgBr 2.9M (9 mL)를 천천히 적가하였다. 30분 후, 건조된 DMF (10mL)을 천천히 적가한 후 실온에서 2시간 동안 교반하였다. 이로부터 얻어진 반응용액에 에틸아세테이트 100 mL를 적가한 후, 물로 여러 번 씻어 낸다. EtOAc를 제거하여 화학식 2d'를 얻었다. 4,4 '-(4,4'-(propane-2,2-diyl) bis (4, l-phenylene)) bis (oxy) dianiline (10 g), NaN02 (4 g), KI (12.1 g) , cone. Using HC1 (20 ml), a solid intermediate (7.7 g) was obtained in the same manner as in Synthesis example 1. The obtained intermediate (5.7 g) was dissolved in Tedra hydrofuran (40 mL), and then slowly added dropwise pro-MgBr 2.9M (9 mL) at -40 ° C. After 30 minutes, dried DMF (10 mL) was slowly added dropwise and stirred at room temperature for 2 hours. 100 mL of ethyl acetate was added dropwise to the reaction solution obtained therefrom, followed by rinsing with water several times. EtOAc was removed to give formula 2d '.
[화학식 2d'
[Formula 2d '
얻어진 화합물 2d'(4.3 g)을 테트라 하이드로 퓨란 (50mL)에 녹인 후 Compound 2d '(4.3 g) obtained was dissolved in tetrahydrofuran (50 mL).
얼음물에서 교반한다. 준비된 용액에 리튬알루미늄 하이드라이드 (0.75 g)을 천천히 적가한 후 얼음물에서 2시간 교반한다. 반응이 완결되면 NaOH 10% Stir in ice water. Lithium aluminum hydride (0.75 g) was slowly added dropwise to the prepared solution, followed by stirring for 2 hours in ice water. NaOH 10% when the reaction is complete
수용액 (0.75 g),H2O(1.5 g),NaOH 10%(2.3g)을 순서대로 천천히 적가한다. Aqueous solution (0.75 g), H 2 O (1.5 g) and NaOH 10% (2.3 g) were added dropwise in order.
상온에서 충분히 교반한 후 필터하여 얻어진 여액을 감압하여 THF를 제거한 후 EtOAc(lOOmL)에 녹인후 물로 여러 번 씻어준다. 남은 유기 용매를 완전히 제거 한 후 중간체 2d"를 얻었다. 얻어진 2d"를 DMF(20mL)에 녹인후 얼음물에서 After sufficiently stirring at room temperature, the filtrate obtained by filtration is depressurized to remove THF, and then dissolved in EtOAc (100 mL) and washed with water several times. After completely removing the remaining organic solvent, intermediate 2d "was obtained. The obtained 2d" was dissolved in DMF (20 mL),
10분간 교반한 후 NaH(60%)를 (1 g)을 천천히 적가한다. 얼음물에서 30분간 교반한 후 프로파질브로마이드 (80%mtolutene)(4mL)를 적가한다. 반웅이 완결되면 EtOAc(lOOmL) 을 넣에 반응액을 희석 시킨 후 물로 여러 번 씻어서 DMF를 제거해 준다. DMF가 완전히 제거 되면 남아있는 EtOAc를 제거해서 화학식 2d로 표현되는 첨가제 (4.5 g)를 얻었다.
화학식 2d]
합성예 5 After stirring for 10 minutes, NaH (60%) was slowly added dropwise (1 g). After stirring for 30 minutes in ice water, propazyl bromide (80% mtolutene) (4 mL) is added dropwise. When the reaction was completed, dilute the reaction solution with EtOAc (100 mL), and wash with water several times to remove DMF. When DMF was completely removed, the remaining EtOAc was removed to obtain an additive (4.5 g) represented by Chemical Formula 2d. Formula 2d] Synthesis Example 5
4,4'-(l,3-phenylenebis(oxy))dianiline (210g), NaN02 (5.7 g), NaCN (4.7 g), cone. HCl (15 ml) 을 사용하여 합성예 1과 동일한 방법을 이용하여 하기 화학식 2e로 표현되는 첨가제를 얻었다. 4,4 '-(l, 3-phenylenebis (oxy)) dianiline (210 g), NaN02 (5.7 g), NaCN (4.7 g), cone. Using HCl (15 ml) using the same method as in Synthesis Example 1 to obtain an additive represented by the following formula (2e).
[화학식 2e]
합성예 6 [Formula 2e] Synthesis Example 6
하기 화학식 2f로 표현되는 첨가제를 준비한다 (TCI사 제조， 제품명 : 2,2- bis[4-(4-aminophenoxy)-phenyl]propanen). An additive represented by the following Chemical Formula 2f is prepared (manufactured by TCI, product name: 2,2-bis (4- (4-aminophenoxy) -phenyl] propanen).
[화학식 2f]
하드마스크 조성물의 제조 [Formula 2f] Preparation of Hard Mask Composition
실시예 1 내지 14， 비교예 1 내지 2 Examples 1 to 14 and Comparative Examples 1 to 2
중합체 및 첨가제를 프로필렌글리콜 모노메틸에테르 아세테이트 (propylene glycol monomethyl ether acetate, PGMEA) 용매에 녹인 후 여과하여 하드마스크 조성물을 제조하였다. The polymer and the additives were dissolved in a propylene glycol monomethyl ether acetate (PGMEA) solvent and filtered to prepare a hard mask composition.
중합체 및 첨가제의 조성은 하기 표 1과 같다. The composition of the polymer and the additive is shown in Table 1 below.
[표 1] TABLE 1
중합체 첨가제 Polymer additives
실시예 1 중합체 la 화학식 2a Example 1 Polymer la Formula 2a
실시예 2 중합체 lb 화학식 2a
실시예 3 중합체 lc 화학식 2a Example 2 Polymer lb Formula 2a Example 3 Polymers lc Formula 2a
실시예 4 중합체 Id 화학식 2b Example 4 Polymer Id Formula 2b
실시예 5 중합체 le 화학식 2b Example 5 Polymer le Formula 2b
실시예 6 중합체 I f 화학식 2a Example 6 Polymer I f Formula 2a
실시예 1 중합체 lg 화학식 2a Example 1 Polymer lg Formula 2a
실시예 8 중합체 lh 화학식 2c Example 8 Polymer lh Formula 2c
실시예 9 중합체 ί 화학식 2a Example 9 Polymers ί Formula 2a
실시예 중합체 lj 화학식 2e EXAMPLES Polymer lj Formula 2e
10 10
실시예 중합체 Id 화학식 2f EXAMPLES Polymer Id Formula 2f
11 11
실시예 증합체 If 화학식 2b Examples Polymers If Formula 2b
12 12
실시예 중합체 lg 화학식 2c EXAMPLES Polymer lg Formula 2c
13 13
실시예 중합체 li 화학식 2d EXAMPLES Polymer li Formula 2d
14 14
비교예 1 중합체 lk - 비교예 2 증합체 la - 비교예 3 중합체 lb - 평가 1: 평탄화 특성 Comparative Example 1 Polymer lk-Comparative Example 2 Polymer la-Comparative Example 3 Polymer lb-Evaluation 1: Flattening Properties
패턴이 형성된 실리콘 웨이퍼 (트렌치 폭 ΙΟμιη, 트렌치 깊이 lOOnm) 위에 표 1에 기재한 조성물을 스핀-온 코팅하여 베이크 공정을 거쳐 박막올 형성한 후 단면을 V-SEM 장비를 이용하여 관찰하였다. After spin-on coating the composition shown in Table 1 on the patterned silicon wafer (trench width ΙΟμιη, trench depth 100nm) to form a thin film through a baking process, the cross section was observed using a V-SEM equipment.
상기 하드마스크 조성물 내의 고형분의 함량은 베어 웨이퍼 상에서의 조성물의 두께가 180 °C에서 120초간 1차 열처리한 후 400 °C에서 120초간 2차 열처리 후에 2000 A가 되도록 조절하였다. 상기 하드마스크 조성물을 스핀-온 코팅하고 이어서, 박막을 180°C에서 120초간 1차 열처리한 후 400 °C에서 120초간 2차 열처리하였다.
평탄화 특성은 홀이 있는 부분과 홀이 없는 부분의 레지스트 하층막의 막두께의 차 (즉, 단차)를 측정하여 관찰한다. 도 1은 코팅액이 도포된 실리콘 웨이퍼에서 임의의 한 패턴을 확대하여 도시한 단면도이다. 도 1에 화살표로 표시한 두께가 단차에 해당한다. The content of solids in the hard mask composition was adjusted so that the thickness of the composition on the bare wafer was 2000 A after the first heat treatment at 180 ° C. for 120 seconds and after the second heat treatment at 400 ° C. for 120 seconds. The hard mask composition was spin-on coated, and then the thin film was subjected to a first heat treatment at 180 ° C. for 120 seconds and then second heat treatment at 400 ° C. for 120 seconds. The planarization characteristic is observed by measuring the difference (that is, the step) between the film thicknesses of the resist underlayer film in the part with holes and without part. 1 is an enlarged cross-sectional view of an arbitrary pattern on a silicon wafer coated with a coating liquid. The thickness indicated by the arrow in FIG. 1 corresponds to the step.
평탄화 특성은 패턴이 있는 부분과 없는 부분의 막 두께의 차이 (단차)가 크지 않을수록 우수한 것이므로 그 수치가 작을수록 평탄화 특성이 우수한 것이다. 그 결과는 표 2에 나타낸 바와 같다. The planarization characteristic is excellent as the difference (step difference) between the film thickness of a part with a pattern and a part without a pattern is so large that a numerical value is so excellent that a planarization characteristic is excellent. The results are as shown in Table 2.
[표 2] TABLE 2
실리콘 웨이퍼 위에 실시예 7 내지 14, 그리고 비교예 1 및 3에 따른 하드마스크 조성물을 상기 하드마스크 조성물을 12인치 실리콘 웨이퍼 위에 스핀-온 코팅하고 이어서, 박막을 180 °C에서 120초간 1차 열처리한 후 400 °C에서 120초간 2차 열처리하였다 . 2차 열처리가 끝나고 난 후의 박막의 두께가 두께가 2,000 A 되도록 고형분의 함량을 조절하였다ᅳ The hard mask composition according to Examples 7 to 14 and Comparative Examples 1 and 3 on a silicon wafer was spin-on-coated the hard mask composition onto a 12 inch silicon wafer, and then the thin film was first heat-treated at 180 ° C. for 120 seconds. After the second heat treatment at 400 ° C for 120 seconds. After the second heat treatment, the solid content was adjusted so that the thickness of the thin film was 2,000 A.
유니포미티는 도 2에 도시한 바와 같이 19개 포인트를 선정하여 , 이들
19개 포인트에서 각각 박막 두께를 측정한 후 하기 계산식 2에 의해 계산하였다, 박막의 두께는 K-MAC 장비를 이용하여 측정하였다. 그 결과는 표 3에 나타낸 바와 같다. Uniformity selects 19 points as shown in FIG. After measuring the thickness of each thin film at 19 points was calculated by the following formula 2, the thickness of the thin film was measured using K-MAC equipment. The results are shown in Table 3.
[계산식 2] [Calculation 2]
유니포미티 (uniformity) (%) = (19개 포인트에서의 박막의 최고 두께 —19개 포인트에서의 박막의 최저 두께) /(19개 포인트에서의 박막의 평균 두께) X 100 Uniformity (%) = (Maximum Thickness of Thin Film at 19 Points—Minimum Thickness of Thin Film at 19 Points) / (Average Thickness of Thin Film at 19 Points) X 100
[표 3] TABLE 3
실리콘 웨이퍼 위에 실시예 1 내지 8， 그리고 비교예 2 및 3에 따른 하드마스크 조성물을 상기 하드마스크 조성물을 스핀-온 코팅하고 이어서, Spin-on coating the hardmask composition with a hardmask composition according to Examples 1-8, and Comparative Examples 2 and 3 on a silicon wafer, and then
180 °C에서 120초간 1차 열처리한 후 4001：에서 120초간 2차 열처리하여 박막을 형성하였다. 2차 열처리가 끝나고 난 후의 박막의 두께가 두께가 2,000 A After the first heat treatment for 120 seconds at 180 ° C. and a second heat treatment for 120 seconds at 4001: to form a thin film. The thickness of the thin film after the second heat treatment is 2,000 A
되도록 고형분의 함량을 조절하였다. The content of solids was adjusted so as to.
제조된 박막의 표면을 전자현미경으로 관찰하였다. 그 결과는 하기 표 4에
나타낸 바와 같다. [표 4]The surface of the prepared thin film was observed with an electron microscope. The results are shown in Table 4 below. As shown. TABLE 4
조성물로부터 형성된 박막은 비교예 2 및 3에 따른 하드마스크 조성물로부터 형성된 박막과 비교하여 코팅성이 우수하였다. 이상에서 본 발명의 바람직한 실시예들에 대하여 상세하게 설명하였지만 본 발명의 권리 범위는 이에 한정되는 것은 아니고 다음의 청구 범위에서 정의하고 있는 본 발명의 기본 개념올 이용한 당업자의 여러 변형 및 개량 형태 또한 본 발명의 권리 범위에 속하는 것이다.
The thin film formed from the composition was superior in coating property as compared with the thin film formed from the hardmask compositions according to Comparative Examples 2 and 3. Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concept of the present invention as defined in the following claims are also provided. It belongs to the scope of the invention.
Claims
【청구항 1】 [Claim 1]
하기 화학식 1로 표현되는 구조단위를 포함하는 중합체， 방향족 고리 함유 화합물로서 그 구조 내에 치환 또는 비치환된 아민기, 치환 또는 비치환된 비닐기 치환 또는 비치환된 아세틸렌기， 아자이드기, 또는 나이트릴기를 적어도 하나 포함하는 첨가제, A polymer comprising a structural unit represented by the following formula (1), an aromatic ring-containing compound, substituted or unsubstituted amine group, substituted or unsubstituted vinyl group substituted or unsubstituted acetylene group, azide group, or nitrate in the structure An additive comprising at least one reel group,
그리고 용매 And solvent
를 포함하는 Containing
유기막 조성물: Organic film composition:
1]
One]
상기 화학식 1에서, In Chemical Formula 1,
A는 치환 또는 비치환된 방향족 고리 함유기, 치환 또는 비치환된 해테로 방향족 고리 함유기, 또는 이들의 조합이고, A is a substituted or unsubstituted aromatic ring containing group, a substituted or unsubstituted heteroaromatic ring containing group, or a combination thereof,
B는 2가의 유기기이고， B is a divalent organic group,
A 및 B 중 적어도 하나는 하기 화학식 2로 표현되는 부분을 포함하는 작용기에 의해 치환된 것이다: At least one of A and B is substituted by a functional group comprising a moiety represented by the following formula (2):
[화학식 2] [Formula 2]
Z는 수소, 히드록시기, 치환 또는 비치환된 C1 내지 C10 알킬기, 또는 치환 또는 비치환된 C6 내지 C30 아릴기이고， Z is hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
*는 연결지점이다. * Is the connection point.
【청구항 2】
제 1항에서, [Claim 2] In claim 1,
상기 화학식 2로 표현되는 부분을 포함하는 작용기는 하기 화학식 2'로 표현되는 것인 유기막 조성물: A functional group comprising a moiety represented by Formula 2 is represented by the following Formula 2 ':
[화학식 2'] [Formula 2 ']
(W)a (W) a
상기 화학식 2'에서, In Chemical Formula 2 ',
W는 0, S, NRa또는 CRbR^l고, 여기서 Ra 내지 ！ 는 각각 독립적으로 수소 치환 또는 비치환된 C1 내지 C10 알킬기， 할로겐 원자， 할로겐 함유기 또는 이들의 조합이고, W is 0, S, NR a or CR b R ^ l, wherein R a to! Are each independently a hydrogen-substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group, or a combination thereof,
Z는 수소, 히드록시기, 치환 또는 비치환된 C1 내지 C10 알킬기 , 또는 치환 또는 비치환된 C6 내지 C30 아릴기이고, Z is hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group,
a는 0 또는 1이고, a is 0 or 1,
b는 0 내지 10의 정수이고, b is an integer from 0 to 10,
*는 연결지점이다. * Is the connection point.
【청구항 3 ] [Claim 3]
거 1항에서, In almost 1 paragraph,
상기 첨가제는 하기 화학식 3으로 표현되는 유기막 조성물: The additive is an organic film composition represented by the following formula (3):
[화학식 3] [Formula 3]
X X
상기 화학식 3에서,
k, m 및 n는 각각 독립적으로 0 또는 1이되 k, m 및 n의 합은 2 또는 3이고 k+m+n=3일 때 X는 -CH- 또는 질소 (N)이고, In Chemical Formula 3, k, m and n are each independently 0 or 1, and the sum of k, m and n is 2 or 3 and when k + m + n = 3, X is -CH- or nitrogen (N),
k+m+n=2일 때 X는 직접결합, -(CqH2q)-, -(CtRw 2t)-, 산소 (0), 황 (S), -NH-, 또는 -S(02)-이고, 여기서 q 및 t는 각각 독립적으로 1 내지 5인 정수이고 Rw는 치환 또는 비치환된 C 1 내지 C20 알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기， 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기, 치환 또는 비치환된 C 1 내지 C20 알킬아민기, 치환 또는 비치환된 C7 내지 C20 아릴알킬기， 치환 또는 When k + m + n = 2, X is a direct bond,-(C q H 2q )-,-(C t R w 2t )-, oxygen (0), sulfur (S), -NH-, or -S (0 2 )-, wherein q and t are each independently an integer of 1 to 5 and R w is a substituted or unsubstituted C 1 to C20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C 1 to C20 alkylamine group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or
비치환된 C1 내지 C20 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 Unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30
헤테로사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기, 치환 또는 비치환된 C 1 내지 C4 알킬 에테르기， 치환 또는 비치환된 C7 내지 C20 아릴알킬렌 에테르기, 치환 또는 비치환된 C 1 내지 C30 할로알킬기, 치환 또는 비치환된 C2 내지 C20 알케닐기, 또는 이들의 조합이고, Heterocycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C 1 to C4 alkyl ether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C 1 To C30 haloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,
R, R'및 R"는 각각 독립적으로 치환 또는 비치환된 방향족 고리 함유기이되. R, R'또는 R" 는 치환 또는 비치환된 아민기, 치환 또는 비치환된 비닐기, 치환 또는 비치환된 아세틸렌기, 아자이드기, 또는 나이트릴기를 적어도 하나 포함한다. 【청구항 4】 R, R 'and R "are each independently a substituted or unsubstituted aromatic ring containing group. R, R' or R" is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted group. At least one acetylene group, azide group, or nitrile group. [Claim 4]
게 3항에서, - 상기 첨가제는 하기 화학식 4 또는 5로 표현되는 유기막 조성물: According to claim 3,-The additive is an organic film composition represented by the following formula (4) or:
[화학식 4] [Formula 4]
[화학식 5] R4— X— R5 [Formula 5] R 4 — X— R 5
상기 화학식 4 및 5에서, In Chemical Formulas 4 and 5,
X1는 -CH- 또는 질소 (N)이고, X 1 is -CH- or nitrogen (N),
X2는 직접결합, -(CqH2q)-, -(CtRw 2t)-, 산소 (0), 황 (S), -NH- 또는 -S(02)-이고, 여기서 q 및 t는 각각 독립적으로 1 내지 5인 정수이고 Rw는 치환 또는 비치환된
CI 내지 C20 알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 치환 또는 비치환된 C3 내지 C30 사이클로알케닐기， 치환 또는 비치환된 C1 내지 C20 알킬아민기, 치환 또는 비치환된 C7 내지 C20 아릴알킬기, 치환 또는 비치환된 C1 내지 C20 헤테로알킬기, 치환 또는 비치환된 C2 내지 C30 X 2 is a direct bond,-(C q H 2q )-,-(C t R w 2t )-, oxygen (0), sulfur (S), -NH- or -S (0 2 )-, wherein q And t are each independently an integer of 1 to 5 and R w is substituted or unsubstituted CI to C20 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C7 to C20 arylalkyl group , Substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30
헤테로사이클로알킬기, 치환 또는 비치환된 C2 내지 C30 헤테로아릴기， 치환 또는 비치환된 C1 내지 C4 알킬 에테르기, 치환 또는 비치환된 C7 내지 C20 아릴알킬렌 에테르기, 치환 또는 비치환된 C1 내지 C30 할로알킬기， 치환 또는 비치환된 C2 내지 C20 알케닐기, 또는 이들의 조합이고, Heterocycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C1 to C4 alkyl ether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted C1 to C30 Haloalkyl group, substituted or unsubstituted C2 to C20 alkenyl group, or a combination thereof,
R1 내지 R5는 각각 독립적으로 하기 화학식 6으로 표현되는 기를 적어도 하나 포함하는 방향족 고리 함유기이다: R 1 to R 5 are each independently an aromatic ring-containing group including at least one group represented by the following formula (6):
[화학식 6] [Formula 6]
(W)a (W) a
상기 화학식 6에서, In Chemical Formula 6,
W는 0, S, NRa또는 CRbRc이고, 여기서 Ra 내지 Rc는 각각 독립적으로 수소 치환 또는 비치환된 C1 내지 C10 알킬기, 할로겐 원자， 할로겐 함유기 또는 이들의 조합이고, W is 0, S, NR a or CR b R c , wherein R a to R c are each independently a hydrogen substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group or a combination thereof,
Y는 치환 또는 비치환된 아민기, 치환 또는 비치환된 비닐기, 치환 또는 비치환된 아세틸렌기， 아자이드기, 나이트릴기, 또는 이들의 조합이고， Y is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, a nitrile group, or a combination thereof,
a는 0 또는 1이고, a is 0 or 1,
b는 0 내지 10의 정수이고, b is an integer from 0 to 10,
*는 연결지점이다. * Is the connection point.
【청구항 5】 [Claim 5]
게 4항에서, In crab 4,
상기 화학식 4 및 5에서, R1 내지 R5는 각각 독립적으로 하기 화학식 7로 표현되는 유기막 조성물:
[화학식 7] In Chemical Formulas 4 and 5, R 1 to R 5 are each independently an organic film composition represented by Formula 7: [Formula 7]
Rla 내지 R13a은 각각 독립적으로 수소, 히드록시기， 치환 또는 비치환된 C1 내지 C10 알킬기, 또는 상기 화학식 6으로 표시되는 기이되， Rla 내지 R13a 중 적어도 하나는 상기 화학식 6으로 표시되는 기이고, R la to R 13a are each independently hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C10 alkyl group, or a group represented by Formula 6, and at least one of R la to R 13a is a group represented by Formula 6 ,
T' 및 τ2는 각각 독립적으로 0, S, NRa 또는 CRbRc이고, 여기서 Ra 내지 Rc는 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 할로겐 원자， 할로겐 함유기 또는 이들의 조합이고， T 'and τ 2 are each independently 0, S, NR a or CR b R c , wherein R a to R c are each independently hydrogen, a substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group Or a combination thereof,
c 및 d는 각각 독립적으로 0 내지 5인 정수이고, c and d are each independently an integer of 0 to 5,
*는 연결지점이다. * Is the connection point.
【청구항 6】 [Claim 6]
제 1항에서, In claim 1,
상기 화학식 1에서, 상기 A는 하기 그룹 1 및 2 중에서 선택된 치환 또는 비치환된 모이어티인 유기막 조성물:
In Formula 1, wherein A is a substituted or unsubstituted moiety selected from Groups 1 and 2 below:
[그룹 1] [Group 1]
상기 그룹 2에서, In group 2 above,
Z1 및 Z2는 각각 독립적으로 NRd, 0, S, Te 또는 Se이고， Z 1 and Z 2 are each independently NR d , 0, S, Te or Se,
Z3 및 Z4는 N이고, Z 3 and Z 4 are N,
Rd 및 Re은 각각 독립적으로 수소, 히드록시기， 메록시기, 에특시기, 할로겐 원자， 할로겐 함유기, 치환 또는 비치환된 1 내지 C30 알킬기， 치환 또는 비치환된 C6 내지 C30 아릴기, 또는 이들의 조합이다.
R d and R e are each independently hydrogen, a hydroxy group, a hydroxy group, a special group, a halogen atom, a halogen containing group, a substituted or unsubstituted 1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or It is a combination.
【청구항 7] [Claim 7]
거 U항에서, In U,
상기 화학식 1에서, 상기 A는 적어도 1개의 치환 또는 비치환된 방향족, 헤테로 방향족 고리를 포함하는 유기막 조성물. In Formula 1, A is an organic film composition comprising at least one substituted or unsubstituted aromatic, heteroaromatic ring.
【청구항 8] [Claim 8]
제 1항에서, In claim 1,
상기 B는 하기 화학식 Z1 내지 화학식 Z4 중 어느 하나로 표현되는 유기막 조성물: The B is an organic film composition represented by any one of the following formula Z1 to formula Z4:
[화학식 Z1] [Formula Z1]
*— (-C 4-— γ 1_ (Ό — * * — (-C 4-— γ 1_ (Ό — *
[화학식 Z2] [Formula Z2]
[화학식 Z3]
[Formula Z3]
H H
[ Z4]
[Z4]
상기 화학식 Z1 내지 Z4에서, In Chemical Formulas Z1 to Z4,
e 및 f는 각각 독립적으로 0 또는 1이고, e and f are each independently 0 or 1,
g는 1 내지 5인 정수이고, g is an integer of 1 to 5,
Y1내지 Y4는 각각 독립적으로 하기 그룹 3에서 선택된 치환 또 비치환된 모이어티 중 어느 하나이고, Y 1 to Y 4 are each independently any one of a substituted or unsubstituted moiety selected from Group 3,
*은 연결지점이다:
[그룹 3] * Is the connection point: [Group 3]
M, M'및 M"는 각각 독립적으로 치환 또는 비치환된 C1 내지 C10 알킬렌기 0, S, S02, CRfRg, NRh, 또는 카르보닐이고, 여기서 Rf 내지 Rh는 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 할로겐 원자， 할로겐 함유기 또는 이들의 조합이고， M, M 'and M "are each independently a substituted or unsubstituted C1 to C10 alkylene group 0, S, S0 2 , CR f R g , NR h , or carbonyl, wherein R f to R h are each independently Hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof,
L1은 치환 또는 비치환된 C6 내지 C50 아릴렌기， 치환 또는 비치환된 C1 내지 C10 알킬렌옥사이드 함유기, 또는 이들의 조합이고, L 1 is a substituted or unsubstituted C6 to C50 arylene group, a substituted or unsubstituted C1 to C10 alkylene oxide containing group, or a combination thereof,
r은 0 내지 10인 정수이고, r is an integer from 0 to 10,
s는 0 내지 10인 정수이고, s is an integer from 0 to 10,
k는 0 내지 3인 정수이다. k is an integer of 0-3.
【청구항 9】 [Claim 9]
제 1항에서, In claim 1,
상기 중합체는 하기 화학식 8로 표현되는 구조단위를 더 포함하는 유기막 조성물:
[화학식 8] The polymer film organic composition further comprises a structural unit represented by the following formula (8): [Formula 8]
― xL_ Lo_ . 상기 화학식 8에서, - xL_ L o_. In Chemical Formula 8,
X0는 치환 또는 비치환된 방향족 고리 함유기, 치환 또는 비치환된 헤테로 방향족 고리 함유기, 또는 이들의 조합이고, X 0 is a substituted or unsubstituted aromatic ring containing group, a substituted or unsubstituted hetero aromatic ring containing group, or a combination thereof,
L0은 2가의 유기기이고, L 0 is a divalent organic group,
*은 연결지점이다. * Is the connection point.
【청구항 10] [Claim 10]
제 9항에서, In claim 9,
상기 화학식 8에서 상기 X0는 하기 그룹 1 및 2 중에서 선택된 치환 또는 비치환된 모이어티인 유기막 조성물: In Formula 8, wherein X 0 is a substituted or unsubstituted moiety selected from Groups 1 and 2 below:
[그룹 1] [Group 1]
상기 그룹 2에서, In group 2 above,
Z1 및 Z2는 각각 독립적으로 NRd, 0, S, Te 또는 Se이고, Z 1 and Z 2 are each independently NR d , 0, S, Te or Se,
Z3 및 Z4는 N이고, Z 3 and Z 4 are N,
Rd 및 Re은 각각 독립적으로 수소, 히드록시기, 메록시기, 에록시기, 할로겐 원자, 할로겐 함유기 , 치환 또는 비치환된 1 내지 C30 알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 또는 이들의 조합이다. R d and R e are each independently hydrogen, hydroxy group, hydroxy group, hydroxy group, halogen atom, halogen containing group, substituted or unsubstituted 1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, or It is a combination.
【청구항 11】 [Claim 11]
제 1항에서, In claim 1,
상기 중합체는 그 구조단위 내에 적어도 하나의 산소 원자를 포함하는 유기막 조성물. And the polymer comprises at least one oxygen atom in its structural unit.
【청구항 12] [Claim 12]
게 1항에서, In crab 1,
상기 화학식 2는 하기 화학식 2'로 표현되는 유기막 조성물:
[화학식 2'] Formula 2 is an organic film composition represented by the following formula 2 ': [Formula 2 ']
(W)a (W) a
상기 화학식 2'에서, In Chemical Formula 2 ',
W는 0, S, NRa또는 CRbRc이고, 여기서 Ra 내지 Rc는 각각 독립적으로 수소， 치환 또는 비치환된 C1 내지 C20 알킬기, 할로겐 원자, 할로겐 함유기 또는 이들의 조합이고, W is 0, S, NR a or CR b R c , wherein R a to R c are each independently hydrogen, a substituted or unsubstituted C 1 to C 20 alkyl group, a halogen atom, a halogen containing group or a combination thereof,
a는 0 또는 1이고, a is 0 or 1,
*는 연결지점이다. * Is the connection point.
【청구항 13] [Claim 13]
게 1항에서， From crab 1
상기 첨가제는 하기 화학식 Y1 내지 Y4 중 어느 하나로 표현되는 유기막 조성물: The additive is an organic film composition represented by any one of the following formula Y1 to Y4:
[화학식 Y1] [Formula Y1]
[화학식 Y2]
[화학식 [Formula Y2] Formula
[화학식 Formula
상기 화학식 Y1 내지 Y4에서, In Chemical Formulas Y1 to Y4,
T3 및 T4는 각각 독립적으로 0, S, NRa 또는 CRbRc이고, 여기서 Ra 내지 Rc는 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 할로겐 원자, 할로겐 함유기 또는 이들의 조합이고, T 3 and T 4 are each independently 0, S, NR a or CR b R c , wherein R a to R c are each independently hydrogen, a substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group Or a combination thereof,
Rx 내지 Ry는 각각 독립적으로 수소, 할로겐 원자, 할로겐 함유기, 또는 치환 또는 비치환된 C1 내지 C20 알킬기이고, R x to R y are each independently hydrogen, a halogen atom, a halogen-containing group, or a substituted or unsubstituted C1 to C20 alkyl group,
R33 내지 R55은 각각 독립적으로 하기 화학식 6으로 표시되는 기이다: R 33 to R 55 are each independently a group represented by the following formula (6):
[화학식 6] [Formula 6]
(W)a (W) a
상기 화학식 6에서, In Chemical Formula 6,
W는 ᄋ, S, NRa 또는 CRbRc이고, 여기서 Ra 내지 Rc는 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C10 알킬기, 할로겐 원자， 할로겐 함유기 또는 이들의 조합이고, W is o , S, NR a or CR b R c , wherein R a to R c are each independently hydrogen, a substituted or unsubstituted C 1 to C 10 alkyl group, a halogen atom, a halogen containing group or a combination thereof,
Y는 치환 또는 비치환된 아민기, 치환 또는 비치환된 비닐기， 치환 또는 비치환된 아세틸렌기， 아자이드기， 나이트릴기， 또는 이들의 조합이고，
a는 0 또는 1이고, Y is a substituted or unsubstituted amine group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted acetylene group, an azide group, a nitrile group, or a combination thereof, a is 0 or 1,
b는 0 내지 10의 정수이고, b is an integer from 0 to 10,
*는 연결지점이다. * Is the connection point.
【청구항 14] [Claim 14]
제 1항에서, In claim 1,
상기 첨가제는 150 내지 50,000의 분자량을 가지는 유기막 조성물. The additive has an organic film composition having a molecular weight of 150 to 50,000.
【청구항 15】 [Claim 15]
제 1항에서， In paragraph 1,
상기 중합체는 500 내지 200,000의 중량평균분자량을 가지는 유기막 조성물. The polymer has an organic film composition having a weight average molecular weight of 500 to 200,000.
【청구항 16】 [Claim 16]
제 1항에서， In paragraph 1,
상기 첨가제는 상기 유기막 조성물의 총 함량에 대하여 5 중량0 /0 내지 50 중량%로 포함되어 있는 유기막 조성물. The additive composition of the organic film, which is provided as a 5 weight 0/0 to 50% by weight relative to the total amount of the organic layer composition.
【청구항 17] [Claim 17]
기판 위에 재료 층을 제공하는 단계, Providing a layer of material over the substrate,
상기 재료 층 위에 제 1항 내지 제 16항 중 어느 한 항에 따른 유기막 조성물을 적용하는 단계, Applying an organic film composition according to any one of claims 1 to 16 on said material layer,
상기 유기막 조성물을 열처리하여 하드마스크 층을 형성하는 단계, 상기 하드마스크 층 위에 실리콘 함유 박막층을 형성하는 단계, Heat treating the organic layer composition to form a hard mask layer, forming a silicon-containing thin film layer on the hard mask layer,
상기 실리콘 함유 박막층 위에 포토레지스트 층을 형성하는 단계, 상기 포토레지스트 층을 노광 및 현상하여 포토레지스트 패턴을 형성하는 단계， Forming a photoresist layer on the silicon-containing thin film layer, exposing and developing the photoresist layer to form a photoresist pattern,
상기 포토레지스트 패턴을 이용하여 상기 실리콘 함유 박막층 및 상기 하드마스크 층을 선택적으로 제거하고 상기 재료 층의 일부를 노출하는 단계, 그리고 Selectively removing the silicon-containing thin film layer and the hardmask layer using the photoresist pattern and exposing a portion of the material layer; and
상기 재료 층의 노출된 부분을 식각하는 단계 Etching the exposed portion of the material layer
를 포함하는 패턴 형성 방법. Pattern forming method comprising a.
【청구항 18] [Claim 18]
제 17항에서, The method of claim 17,
상기 유기막 조성물을 적용하는 단계는 스핀-온 코팅 방법으로 수행하는
패턴 형성 방법. Applying the organic film composition is performed by a spin-on coating method Pattern formation method.
【청구항 19] [Claim 19]
제 17항에서, The method of claim 17,
상기 열처리는 50 내지 250 °C에서 진행되는 게 1차 열처리, 그리고 상기 제 1 열처리에 후속되고 200 내지 500 °C에서 진행되는 게 2차 열처리를 포함하는 패턴 형성 방법. The heat treatment to the primary heat treatment, and a method of forming patterns to include a secondary heat treatment subsequent to said first thermal treatment is conducted at 200 to 500 ° C is conducted at 50 to 250 ° C.
【청구항 20】 [Claim 20]
제 17항에서, The method of claim 17,
상기 포토레지스트 층을 형성하는 단계 전에 바닥 반사 방지 층 (BARC)을 형성하는 단계를 더 포함하는 패턴 형성 방법.
And forming a bottom antireflective layer (BARC) before forming the photoresist layer.
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| KR20090004969A (en) * | 2006-03-29 | 2009-01-12 | 스미토모 베이클리트 컴퍼니 리미티드 | Resin composition, varnish, resin film, and semiconductor device using the resin film |
| JP2009014816A (en) * | 2007-07-02 | 2009-01-22 | Jsr Corp | Resist lower layer film forming composition and pattern forming method |
| CN101693667A (en) * | 2009-10-23 | 2010-04-14 | 中国科学院化学研究所 | Perfume fouramine and derivant thereof and preparation method and application thereof |
| KR20150131867A (en) * | 2014-05-16 | 2015-11-25 | 제일모직주식회사 | Hardmask composition and method of forming patterns using the hardmask composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3521332A4 (en) * | 2016-11-10 | 2020-06-17 | Samsung SDI Co., Ltd. | Polymer, organic film composition, and method for forming pattern |
| US11203662B2 (en) | 2016-11-10 | 2021-12-21 | Samsung Sdi Co., Ltd. | Polymer, organic layer composition, and method of forming patterns |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109478015B (en) | 2022-04-12 |
| TW201804256A (en) | 2018-02-01 |
| CN109478015A (en) | 2019-03-15 |
| KR102296794B1 (en) | 2021-08-31 |
| TWI639056B (en) | 2018-10-21 |
| KR20180013104A (en) | 2018-02-07 |
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