CN112384596B - Etching composition for silicon nitride film and method for etching semiconductor device - Google Patents
Etching composition for silicon nitride film and method for etching semiconductor device Download PDFInfo
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- CN112384596B CN112384596B CN201980046316.5A CN201980046316A CN112384596B CN 112384596 B CN112384596 B CN 112384596B CN 201980046316 A CN201980046316 A CN 201980046316A CN 112384596 B CN112384596 B CN 112384596B
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- 238000005530 etching Methods 0.000 title claims abstract description 120
- 239000000203 mixture Substances 0.000 title claims abstract description 64
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 52
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000004065 semiconductor Substances 0.000 title claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 103
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 33
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 34
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 34
- -1 silane compound Chemical class 0.000 abstract description 24
- 229910000077 silane Inorganic materials 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 230000002269 spontaneous effect Effects 0.000 abstract description 11
- 238000001556 precipitation Methods 0.000 abstract description 9
- 125000000217 alkyl group Chemical group 0.000 description 16
- 125000003545 alkoxy group Chemical group 0.000 description 13
- 125000002947 alkylene group Chemical group 0.000 description 13
- 125000003118 aryl group Chemical group 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 11
- 125000005843 halogen group Chemical group 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 125000000753 cycloalkyl group Chemical group 0.000 description 8
- 125000001072 heteroaryl group Chemical group 0.000 description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical group C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 7
- 125000002723 alicyclic group Chemical group 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 125000000304 alkynyl group Chemical group 0.000 description 6
- 125000004366 heterocycloalkenyl group Chemical group 0.000 description 6
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 125000002843 carboxylic acid group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- 125000003396 thiol group Chemical group [H]S* 0.000 description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 125000002993 cycloalkylene group Chemical group 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 125000006588 heterocycloalkylene group Chemical group 0.000 description 4
- 229910001867 inorganic solvent Inorganic materials 0.000 description 4
- 239000003049 inorganic solvent Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000002619 bicyclic group Chemical group 0.000 description 3
- 125000004446 heteroarylalkyl group Chemical group 0.000 description 3
- 125000005549 heteroarylene group Chemical group 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000005417 glycidoxyalkyl group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- YATIYDNBFHEOFA-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-ol Chemical compound CO[Si](OC)(OC)CCCO YATIYDNBFHEOFA-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229960002050 hydrofluoric acid Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- IJQHYEFNLXHUGV-UHFFFAOYSA-N trimethoxysilylmethyl acetate Chemical compound CO[Si](OC)(OC)COC(C)=O IJQHYEFNLXHUGV-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
-
- 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Weting (AREA)
Abstract
Provided are an etching composition for a silicon nitride film and a method for etching a semiconductor device. The etching composition includes: an inorganic acid or salt thereof; water; and at least one of the following compounds: a compound of formula 1, a compound of formula 2, and a reaction product of the compound of formula 1 or the reaction product of the compound of formula 2. R of formula 1 or formula 2 1 、R 2 、R 3 、R 6 、R 9 To R 12 The definitions of (a) are the same as those described in the present specification. The etching composition for a silicon nitride layer can significantly improve the etching selectivity of a silicon nitride layer with respect to a silicon oxide layer and can prevent an increase in the thickness of the silicon oxide layer or precipitation of a silane compound by a spontaneous reaction during and/or after etching.
Description
Technical Field
The present invention relates to an etching composition for a silicon nitride layer and a method for etching a semiconductor device. More particularly, the present invention relates to an etching composition for a silicon nitride layer comprising a silane compound of formula 1, a compound of formula 2, and at least one of a reaction product of the compound of formula 1 or a reaction product of the compound of formula 2, to achieve a significant increase in etching selectivity of the silicon nitride layer with respect to the silicon oxide layer while preventing an increase in thickness of the silicon oxide layer during and/or after etching or precipitation of the silane compound by a spontaneous reaction, and a method of etching a semiconductor device.
Background
The silicon nitride layer is formed on the upper surface or the lower surface of the silicon oxide layer, or alternately stacked with the silicon oxide layer.
As known in the art, there is an etching method using a phosphoric acid solution heated to a high temperature in order to remove a silicon nitride layer pattern formed on a substrate in a semiconductor manufacturing process. However, the phosphoric acid solution has a limitation in improving the etching selectivity of the silicon nitride layer with respect to the silicon oxide layer. It is believed that the use of silane compounds improves etch selectivity.
Tetraethoxysilane can be used as the silane compound. However, tetraethoxysilane still has a limitation in improving etching selectivity, and precipitates itself by accumulation on a silicon oxide layer during or after etching (abnormal growth) or by spontaneous reaction.
Disclosure of Invention
Technical challenge
An object of the present invention is to provide an etching composition for a silicon nitride layer, which can significantly improve the etching selectivity of a silicon nitride layer with respect to a silicon oxide layer.
Another object of the present invention is to provide an etching composition for a silicon nitride layer, which can prevent an increase in the thickness of a silicon oxide layer or precipitation of a silane compound by a spontaneous reaction during and/or after etching.
It is still another object of the present invention to provide a method for etching a semiconductor device, which can significantly improve the etching selectivity of a silicon nitride layer with respect to a silicon oxide layer, and can prevent an increase in the thickness of the silicon oxide layer or precipitation of a silane compound by a spontaneous reaction during and/or after etching.
Means for solving the problems
According to one embodiment of the present invention, an etching composition for a silicon nitride layer includes: an inorganic acid or salt thereof; water; and at least one of the following compounds: a compound of formula 1; a compound of formula 2; and a reaction product of a compound of formula 1 or a reaction product of a compound of formula 2:
[ formula 1]
Wherein R is 1 、R 2 、R 3 And R 6 As defined in the embodiments of the present invention; and
[ formula 2]
(wherein R is 9 、R 10 、R 11 And R 12 As defined in the embodiments of the present invention)
In one embodiment, R 1 、R 2 And R 3 Can each be C 1 To C 10 An alkoxy group.
In one embodiment, the compound of formula 1 may include at least one of acetoxyalkyltrialkoxysilane, benzoyloxyalkyltrialkoxysilane, (alkoxycarbonyl) alkyltrialkoxysilane, and hydroxyalkyltrialkoxysilane.
In one embodiment, R 9 、R 10 And R 11 Can be respectively C 1 To C 10 An alkoxy group.
In one embodiment, in formula 2, the epoxidized aliphatic hydrocarbon group may be a glycidoxy group, and the epoxidized alicyclic hydrocarbon group may be an epoxycyclohexyl group.
In one embodiment, the compound of formula 2 may include at least one of a glycidoxyalkyltrialkoxysilane, a (glycidoxyalkyl) alkyldialkoxysilane, and an epoxycyclohexylalkyltrialkoxysilane.
In one embodiment, at least one of the compound of formula 1, the compound of formula 2, and the reaction product of the compound of formula 1 or the reaction product of the compound of formula 2 may be present in the etching composition for a silicon nitride layer in an amount of about 0.00001 wt% to about 25 wt%.
In one embodiment, the mineral acid can be phosphoric acid.
According to another aspect of the present invention, a method for etching a semiconductor device includes etching a silicon nitride layer using the etching composition for a silicon nitride layer as described above.
Technical effects
The present invention provides an etching composition for a silicon nitride layer, which can significantly improve the etching selectivity of a silicon nitride layer with respect to a silicon oxide layer.
The present invention provides an etching composition for a silicon nitride layer, which can prevent an increase in the thickness of a silicon oxide layer or precipitation of a silane compound by a spontaneous reaction during and/or after etching.
The present invention provides a method for etching a semiconductor device, which can significantly improve the etching selectivity of a silicon nitride layer with respect to a silicon oxide layer, and can prevent an increase in the thickness of the silicon oxide layer or precipitation of a silane compound by a spontaneous reaction during and/or after etching.
Detailed Description
Numerical ranges (e.g., C) herein 1 To C 10 Alkyl) includes not only each numerical value within that range, but also includes all ranges within that range. For example, "C 1 To C 10 Alkyl "may include C 1 、C 2 、C 3 、C 4 、C 5 、C 6 、C 7 、C 8 、C 9 、C 10 、C 2 To C 10 、C 3 To C 10 Or C 1 To C 2 An alkyl group.
"alkyl" refers to a saturated straight or branched carbon chain having the indicated number of carbon atoms.
"alkenyl" refers to an unsaturated straight or branched chain alkyl group having the indicated number of carbon atoms and at least one carbon-carbon double bond derived by the removal of one hydrogen atom from each of the adjacent carbon atoms of the corresponding alkyl group.
"alkynyl" refers to an unsaturated straight or branched chain alkyl group having the indicated number of carbon atoms and at least one carbon-carbon triple bond derived by the removal of two hydrogen atoms from adjacent carbon atoms of the corresponding alkyl group, respectively.
"cycloalkyl" refers to a fully saturated nonaromatic carbocyclic ring having the specified number of carbon atoms. Cycloalkyl groups can be monocyclic or polycyclic (e.g., bicyclic or tricyclic) alkyl groups.
"cycloalkenyl" refers to a fully saturated non-aromatic carbocyclic ring having the indicated number of carbon atoms and at least one carbon-carbon double bond derived by the removal of one hydrogen atom from each of the adjacent carbon atoms of the corresponding cycloalkyl group. Cycloalkenyl groups can be monocyclic or polycyclic (e.g., bicyclic or tricyclic) alkenyl groups.
"aryl" refers to an aromatic carbocyclic ring having the indicated number of carbon atoms. The aryl group can be a monocyclic or polycyclic (e.g., bicyclic or tricyclic) aryl group.
"arylalkyl" refers to a residue having the specified number of carbon atoms and containing an aryl moiety connected to the parent structure through an alkyl residue. The alkyl residue may have a straight chain or a branched chain.
In "heterocycloalkyl", "heterocycloalkenyl", "heteroaryl" and "heteroarylalkyl", hetero (hetero) "refers to a functional group in which the carbon atoms of the functional group are substituted with an atom selected from N, O or S.
"halogen" means F, cl, br or I.
As used herein, "substituted" in the expression "substituted or unsubstituted" refers to the corresponding functional groupIs substituted with at least one hydrogen atom selected from: halogen atom, hydroxyl group, thiol group, cyano group, amine group, carboxylic acid group, sulfonic acid group, phosphoric acid group, phosphonic acid group, azole group, (= O) (R) 4 )、*-C(＝O)-N(R 4 )(R 5 )、*-C(＝O)-O-C(＝O)(R 4 )、C 1 To C 10 Alkyl radical, C 2 To C 10 Alkenyl radical, C 2 To C 10 Alkynyl, C 1 To C 10 Alkoxy radical, C 3 To C 10 Cycloalkyl, C 1 To C 10 Heterocycloalkyl, C 3 To C 10 Cycloalkenyl radical, C 1 To C 10 Heterocycloalkenyl, C 6 To C 20 Aryl and C 1 To C 20 A heteroaryl group.
The present inventors completed the present invention based on the following findings: when the etching composition for a silicon nitride layer, which comprises an inorganic acid or a salt thereof and water, further comprises at least one of a compound of formula 1, a compound of formula 2, and a reaction product of the compound of formula 1 or a reaction product of the compound of formula 2 as a silane-based compound, the etching composition significantly improves the ratio of the etching rate of the silicon nitride layer to the etching rate of the silicon oxide layer (etching selectivity), which does not increase the thickness of the silicon oxide layer (abnormal growth) by preventing the compound of formula 1, the compound of formula 2, or the reaction product of the compound of formula 1 or the compound of formula 2 from accumulating on the surface of the silicon oxide layer during or after etching, and prevents the compound of formula 1, the compound of formula 2, or the reaction product of the compound of formula 1 or the compound of formula 2 from precipitating on the surface of the silicon oxide layer by spontaneous reaction thereof.
Hereinafter, the composition of the etching composition for a silicon nitride layer according to the present invention will be described in more detail.
The inorganic acid or a salt thereof may be selected from any inorganic acid as long as the inorganic acid can provide hydrogen ions to the etching composition. For example, the inorganic acid may include sulfuric acid, nitric acid, hydrochloric acid, perchloric acid, fluoric acid, boric acid, phosphoric acid (H) 3 PO 4 ) Phosphorous acid (H) 3 PO 3 ) Hypophosphorous acid (H) 3 PO 2 ) Hypophosphorous acid (H) 4 P 2 O 6 )、Tripolyphosphoric acid (H) 5 P 3 O 10 ) And pyrophosphoric acid (H) 4 P 2 O 7 ) At least one of (a). Preferably, the inorganic acid is phosphoric acid.
The inorganic acid or salt thereof may be present in the etching composition in an amount of about 60 wt% to about 99.99 wt%. Within this range, the etching composition can improve the ratio of the etching rate of the silicon nitride layer to the etching rate of the silicon oxide layer (etching selectivity). For example, the inorganic acid or salt thereof may be present in the etching composition in an amount of about 60 wt% to about 95 wt%. Alternatively, the inorganic acid or salt thereof may be present in an amount from about 80% to about 90% by weight. For example, the inorganic acid or salt thereof can be present in an amount of 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or 99.99 weight percent.
The water may be, for example, water having a semiconductor grade or ultrapure water, but is not limited thereto. Water may be present in the balance in the etching composition for the silicon nitride layer.
As the silane-based compound, the etching composition may include a compound of formula 1:
[ formula 1]
(in formula 1R 1 、R 2 And R 3 Each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a cyano group, an amine group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, an azole group, and a-C (= O) (R) 4 )、*-C(＝O)-N(R 4 )(R 5 )、*-C(＝O)-O-C(＝O)(R 4 )、C 1 To C 10 Alkyl radical, C 2 To C 10 Alkenyl radical, C 2 To C 10 Alkynyl, C 1 To C 10 Alkoxy radical, C 3 To C 10 Cycloalkyl radical, C 1 To C 10 Heterocycloalkyl, C 3 To C 10 Cycloalkenyl radical, C 1 To C 10 Heterocycloalkenyl, C 6 To C 20 Aryl and C 1 To C 20 A heteroaryl group;
R 4 and R 5 Each independently selected from a hydrogen atom, a halogen atom, C 1 To C 10 Alkyl radical, C 2 To C 10 Alkenyl radical, C 2 To C 10 Alkynyl, C 1 To C 10 Alkoxy radical, C 3 To C 10 Cycloalkyl radical, C 1 To C 10 Heterocycloalkyl radical, C 3 To C 10 Cycloalkenyl radical, C 1 To C 10 Heterocycloalkenyl, C 6 To C 20 Aryl and C 1 To C 20 A heteroaryl group;
R 1 、R 2 and R 3 At least one of which is selected from the group consisting of a halogen atom, a hydroxyl group, a thiol group, a cyano group, an amine group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, an azole group, and-C (= O) (R) 4 )、*-C(＝O)-N(R 4 )(R 5 )、*-C(＝O)-O-C(＝O)(R 4 ) A and C 1 To C 10 An alkoxy group; and is
R 6 Is a group having formula 1-1 or formula 1-2:
[ formula 1-1]
R 8 -A-R 7 -*
(in formula 1-1,. Is a linkage site to Si in formula 1,
a is- (C = O) -O-or-O- (C = O) -, wherein A is a linking site,
R 7 is substituted or unsubstituted C 1 To C 10 Alkylene, substituted or unsubstituted C 3 To C 10 Cycloalkylene, substituted or unsubstituted C 2 To C 10 Heterocycloalkylene, substituted or notSubstituted C 6 To C 20 Arylene, substituted or unsubstituted C 3 To C 20 Heteroarylene, substituted or unsubstituted C 7 To C 20 Arylenealkyl or substituted or unsubstituted C 3 To C 20 Heteroarylene alkyl, and
R 8 is substituted or unsubstituted C 1 To C 10 Alkyl, substituted or unsubstituted C 3 To C 10 Cycloalkyl, substituted or unsubstituted C 2 To C 10 Heterocycloalkyl, substituted or unsubstituted C 6 To C 20 Aryl, substituted or unsubstituted C 3 To C 20 Heteroaryl, substituted or unsubstituted C 7 To C 20 Arylalkyl, or substituted or unsubstituted C 3 To C 20 Heteroarylalkyl group)
[ formulas 1-2]
R 14 -B-R 13 -*
(in the formula 1-2,. Is connected with the Si in the formula 1,
b is-O-, wherein is a linking site,
R 13 is substituted or unsubstituted C 1 To C 10 Alkylene, substituted or unsubstituted C 3 To C 10 Cycloalkylene, substituted or unsubstituted C 2 To C 10 Heterocycloalkylene, substituted or unsubstituted C 6 To C 20 Arylene, substituted or unsubstituted C 3 To C 20 Heteroarylene, substituted or unsubstituted C 7 To C 20 Arylenealkyl or substituted or unsubstituted C 3 To C 20 A heteroarylene alkyl group,
R 14 is a hydrogen atom, substituted or unsubstituted C 1 To C 10 Alkyl, substituted or unsubstituted C 3 To C 10 Cycloalkyl, substituted or unsubstituted C 2 To C 10 Heterocycloalkyl, substituted or unsubstituted C 6 To C 20 Aryl, substituted or unsubstituted C 3 To C 20 Heteroaryl, substituted or unsubstituted C 7 To C 20 Arylalkyl, or substituted or unsubstituted C 3 To C 20 (ii) a heteroaryl alkyl group, wherein,
wherein the conditions are as follows: r is 14 Is a hydrogen atom, or R 13 And R 14 At least one of which is substituted with a hydroxyl group).
In one embodiment, R 1 、R 2 And R 3 At least one of which may be C 1 To C 10 An alkoxy group. In one embodiment, R 1 、R 2 And R 3 Can be C 1 To C 10 An alkoxy group. In one embodiment, R 1 、R 2 And R 3 Can each be C 1 To C 10 An alkoxy group.
In one embodiment, a may be — (C = O) -O-. Here, R 7 C which may be substituted or unsubstituted 1 To C 10 Alkylene, substituted or unsubstituted C 3 To C 10 Cycloalkylene or substituted or unsubstituted C 2 To C 10 A heterocycloalkylene group. In one embodiment, R 7 C which may be substituted or unsubstituted 1 To C 10 An alkylene group. In one embodiment, R 7 C which may be substituted or unsubstituted 1 To C 5 An alkylene group.
In one embodiment, a may be — (C = O) -O-. Here, R 8 C which may be substituted or unsubstituted 1 To C 10 Alkyl or substituted or unsubstituted C 6 To C 20 And (4) an aryl group. In one embodiment, R 8 C which may be substituted or unsubstituted 1 To C 5 An alkyl group. In one embodiment, R 8 C which may be substituted or unsubstituted 6 To C 10 And (3) an aryl group.
In one embodiment, a may be-O- (C = O) -. Here, R 7 C which may be substituted or unsubstituted 1 To C 10 Alkylene, substituted or unsubstituted C 3 To C 10 Cycloalkylene or substituted or unsubstituted C 2 To C 10 A heterocycloalkylene group. In one embodiment, R 7 C which may be substituted or unsubstituted 1 To C 10 An alkylene group. In one embodiment, R 7 C which may be substituted or unsubstituted 1 To C 5 An alkylene group.
In one embodiment, a may be-O- (C = O) -. Here, R 8 C which may be substituted or unsubstituted 1 To C 10 Alkyl, substituted or unsubstituted C 3 To C 10 Cycloalkyl or substituted or unsubstituted C 2 To C 10 A heterocycloalkyl group. In one embodiment, R 8 C which may be substituted or unsubstituted 1 To C 10 An alkyl group. In one embodiment, R 8 C which may be substituted or unsubstituted 1 To C 5 An alkyl group.
In one embodiment, in formulas 1-2, R 13 C which may be substituted or unsubstituted 1 To C 10 Alkylene, and R 14 Is a hydrogen atom.
In one embodiment, the compound of formula 1 may include at least one selected from the group consisting of: acetoxyalkyltrialkoxysilanes including acetoxymethyltrialkoxysilane, acetoxyethyltrialkoxysilane, acetoxypropyltrialkoxysilane, and the like; benzoyloxyalkyltrialkoxysilanes, including benzoyloxypropyltrialkoxysilane and the like; (alkoxycarbonyl) alkyltrialkoxysilanes including 2- (carbomethoxy) ethyltrialkoxysilane and the like; and hydroxyalkyl trialkoxysilanes, including hydroxypropyl trimethoxysilane and the like.
As the silane compound, the etching composition may include a compound of formula 2:
[ formula 2]
(in the formula 2, the first reaction solution,
R 9 、R 10 and R 11 Each independently selected from a hydrogen atom, a halogen atom, a hydroxyl groupThiol, cyano, amine, carboxylic acid, sulfonic acid, phosphoric acid, phosphonic acid, azole, and-C (= O) (R) 4 )、*-C(＝O)-N(R 4 )(R 5 )、*-C(＝O)-O-C(＝O)(R 4 )、C 1 To C 10 Alkyl radical, C 2 To C 10 Alkenyl radical, C 2 To C 10 Alkynyl, C 1 To C 10 Alkoxy radical, C 3 To C 10 Cycloalkyl, C 1 To C 10 Heterocycloalkyl radical, C 3 To C 10 Cycloalkenyl radical, C 1 To C 10 Heterocycloalkenyl, C 6 To C 20 Aryl and C 1 To C 20 Heteroaryl, wherein x is the attachment site to Si in formula 2;
R 4 and R 5 Each independently selected from a hydrogen atom, a halogen atom, C 1 To C 10 Alkyl radical, C 2 To C 10 Alkenyl radical, C 2 To C 10 Alkynyl, C 1 To C 10 Alkoxy radical, C 3 To C 10 Cycloalkyl radical, C 1 To C 10 Heterocycloalkyl radical, C 3 To C 10 Cycloalkenyl radical, C 1 To C 10 Heterocycloalkenyl, C 6 To C 20 Aryl and C 1 To C 20 A heteroaryl group; and is provided with
R 12 Is substituted or unsubstituted C 1 To C 10 An alkylene group having an epoxidized aliphatic hydrocarbon group or an epoxidized alicyclic hydrocarbon group, and containing or not containing at least one oxygen atom in the alkylene chain).
In formula 2, R 12 The "epoxidized aliphatic hydrocarbon group" and the "epoxidized alicyclic hydrocarbon group" may be present in C 1 To C 10 In the alkylene chain of the alkylene group or at the terminal of the alkylene chain thereof.
In formula 2, R 12 By "epoxidized aliphatic hydrocarbon group" is meant a functional group having an epoxidized carbon-carbon bond which constitutes an aliphatic hydrocarbon group. For example, the epoxidized aliphatic hydrocarbon group can be a glycidyloxy group, but is not limited thereto.
In formula 2, R 12 The "epoxidized alicyclic hydrocarbon group" means a compound having an epoxidized carbon atom constituting the alicyclic hydrocarbon groupFunctional group of carbon bond. For example, the epoxidized cycloaliphatic hydrocarbon group can be epoxidized C 5 To C 10 An alicyclic hydrocarbon group. For example, the epoxidized alicyclic hydrocarbon group may be an epoxycyclohexyl group, an epoxycycloheptyl group or an epoxycyclopentyl group, but is not limited thereto.
In formula 2, R 12 C of (A) 1 To C 10 "C" of alkylene 1 To C 10 "means that the number of carbon atoms other than those included in the epoxidized aliphatic hydrocarbon group or the epoxidized alicyclic hydrocarbon group is from 1 to 10.
In one embodiment, R 9 、R 10 And R 11 At least one of which may be selected from halogen atoms, hydroxyl groups, thiol groups, cyano groups, amine groups, carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, phosphonic acid groups, azole groups, (= O) (R) 4 )、*-C(＝O)-N(R 4 )(R 5 )、*-C(＝O)-O-C(＝O)(R 4 ) A and C 1 To C 10 An alkoxy group.
In one embodiment, R 9 、R 10 And R 11 One of them may be C 1 To C 10 An alkoxy group. In one embodiment, R 9 、R 10 And R 11 Two of (A) may be C 1 To C 10 An alkoxy group. In one embodiment, R 9 、R 10 And R 11 Can be respectively C 1 To C 10 Alkoxy groups).
In one embodiment, the compound of formula 2 may include at least one of: glycidoxyalkyltrialkoxysilanes including (3-glycidoxypropyl) trialkoxysilane and the like; (glycidoxyalkyl) alkyldialkoxysilanes including (3-glycidoxypropyl) methyldialkoxysilane and the like; and epoxycyclohexylalkyltrialkoxysilanes, including 2- (3, 4-epoxycyclohexyl) ethyltrialkoxysilane and the like.
The reaction product of the compound of formula 1 or the compound of formula 2 refers to a component derived from the compound of formula 1 or the compound of formula 2. The reaction product may include, for example, a reaction product of each of the compound of formula 1 and the compound of formula 2; a compound of formula 1 or a compound of formula 2 with an inorganic acidOr a reaction product of a salt thereof; a reaction product of a compound of formula 1 or a compound of formula 2 with water; or a reaction product of a compound of formula 1 or a compound of formula 2 with an inorganic acid or a salt thereof and water. Since the compound of formula 1 or the compound of formula 2 may include a halogen atom, a hydroxyl group, a thiol group, a cyano group, an amine group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, an azole group, a-C (= O) (R) 4 )、*-C(＝O)-N(R 4 )(R 5 )、*-C(＝O)-O-C(＝O)(R 4 ) And C 1 To C 10 Alkoxy group, and thus the compound of formula 1 or the compound of formula 2 may be reacted with the compound of formula 1 or the compound of formula 2 adjacent thereto, an inorganic acid or a salt thereof, and/or water. For example, when the compound of formula 1 (or the compound of formula 2) includes a hydroxyl group, dehydration occurs between the compound of formula 1 (or the compound of formula 2) and the compound of formula 1 (or the compound of formula 2) adjacent thereto or between the compound of formula 1 (or the compound of formula 2) and an inorganic acid or a salt thereof to form a reaction product including an ether bond. In another example, when the compound of formula 1 (or the compound of formula 2) includes a halo group or an alkoxy group, a reaction product in which the halo group or the alkoxy group of the compound of formula 1 (or the compound of formula 2) is converted into a hydroxyl group may be formed by a reaction between the compound of formula 1 (or the compound of formula 2) and water. In addition, the compound of formula 1 (or the compound of formula 2) including a hydroxyl group generated by reaction with water may form a reaction product having an ether bond by dehydration with the compound of formula 1 (or the compound of formula 2) adjacent thereto or with an inorganic acid or a salt thereof. As such, various reaction products may be formed and can be readily prepared by one skilled in the art from the functional groups of the compound of formula 1 or the compound of formula 2, the inorganic acid or salt thereof, and/or water.
At least one of the compound of formula 1, the compound of formula 2, and the reaction product of the compound of formula 1 or the reaction product of the compound of formula 2 may be present in the etching composition in an amount of about 0.00001 wt% to about 25 wt%. Within this range, the etching composition can significantly increase the etching selectivity and can prevent abnormal growth and precipitation by spontaneous reaction. For example, at least one of the compound of formula 1, the compound of formula 2, and the reaction product of the compound of formula 1 or the reaction product of the compound of formula 2 may be present in the etching composition in an amount of about 0.001 wt% to about 10 wt%, 0.01 about wt% to about 5 wt%, or about 0.1 wt% to about 3 wt%. For example, at least one of the compound of formula 1, the compound of formula 2, and the reaction product of the compound of formula 1 or the reaction product of the compound of formula 2 may be present in an amount of about 0.00001 wt%, 0.00005 wt%, 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, or 25 wt%.
The etching composition may further include at least one of an organic solvent and an inorganic solvent to improve the solubility of the compound of formula 1, the compound of formula 2, and/or the reaction product of the compound of formula 1 or the compound of formula 2. The organic and inorganic solvents may be selected from any of the organic and inorganic solvents typical in the art and may include, for example, 1-methoxy-2-propanol and propylene glycol methyl ether acetate and the like. In one embodiment, the organic or inorganic solvent may have a boiling point of about 100 ℃ to about 150 ℃ (e.g., about 100 ℃) at 1 atmosphere, but is not limited thereto.
The etching composition for the silicon nitride layer may further include typical additives to improve the etching performance. For example, the etching composition may further include a preservative, a surfactant, a dispersant, and an etching rate modifier, but is not limited thereto.
Methods for etching a semiconductor device may include etching a silicon nitride layer using an etching composition according to the present invention.
The etching method may, for example, include: forming a silicon nitride layer or a silicon oxide layer on a substrate; applying the etching composition to the silicon nitride layer or the silicon oxide layer to perform etching; and removing the etching composition after the etching.
The substrate may be any substrate commonly used in the art, and may be, for example, a semiconductor wafer.
The step of applying the etching composition to the silicon nitride layer or the silicon oxide layer for etching may include, for example: the silicon nitride layer or the silicon oxide layer is immersed in an etching bath containing an etching composition, or the etching composition is sprayed to the upper surface of the silicon nitride layer or the silicon oxide layer, but is not limited thereto.
The etching method may further include heating the etching composition before applying the etching composition to the silicon nitride layer or the silicon oxide layer for etching. Here, the etching composition may be heated to about 100 ℃ or above about 100 ℃, for example, about 100 ℃ to about 500 ℃. In one embodiment, the etching composition may be heated to a temperature of about 150 ℃ to about 300 ℃, but is not limited thereto.
The step of removing the etching composition after etching may include, for example, washing the etching composition with ultra-pure water, followed by drying the silicon oxide layer or the silicon nitride layer, but is not limited thereto.
Modes for carrying out the invention
Next, the present invention will be explained in more detail with reference to examples. It should be noted, however, that these examples are provided for illustration only and should not be construed as limiting the invention in any way.
Example 1
An etching composition for a silicon nitride layer containing 85 wt% of phosphoric acid, 0.5 wt% of acetoxymethyltrimethoxysilane as a silane compound, and the balance water was prepared.
Examples 2 to 8
An etching composition for a silicon nitride layer was prepared in the same manner as in example 1, except that the kind and amount of the silane compound were changed as listed in table 1.
Examples 9 to 14
An etching composition for a silicon nitride layer was prepared in the same manner as in example 1, except that the kind and amount of the silane compound were changed as listed in table 2.
Comparative examples 1 to 8
An etching composition for a silicon nitride layer was prepared in the same manner as in example 1, except that the kind and amount of the silane compound were changed as listed in tables 1 and 2.
The etching compositions for silicon nitride layers prepared in examples and comparative examples were evaluated with respect to the properties listed in tables 1 and 2.
Each of the etching compositions prepared in examples and comparative examples was placed in a beaker and heated to 160 ℃. Then, an LP-SiN film (silicon nitride film formed by a low-pressure CVD method) or a PE-SiO film (silicon oxide film formed by a plasma-enhanced CVD method) was placed therein and etched for 5 minutes using the etching composition. The thickness of the LP-SiN film or PE-SiO film was measured using an ellipsometer before and after etching, and then the etching rate (a) of the silicon nitride layer and the etching rate (B) of the silicon oxide layer were calculated. Then, the etching selectivity was calculated according to equation 1, and the calculation results are shown in tables 1 and 2.
[ equation 1]
Etch selectivity = a/B
Where a represents an etching rate (unit: angstrom/minute) of the etching composition per unit time with respect to the silicon nitride layer, and B represents an etching rate (unit: angstrom/minute) of the etching composition per unit time with respect to the silicon oxide layer.
After each of the etching compositions prepared in examples and comparative examples was heated to 160 ℃, the LP-SiN film or PE-SiO film was etched using the heated etching compositions. After etching, the etching composition was placed in a vial, and then transmittance of the etching composition at a wavelength of 880 nm was measured using a terbiscan (Turbiscan) to determine whether or not precipitates were present in the etching composition, and the results are shown in tables 1 and 2.
[ Table 1]
[ Table 2]
* In tables 1 and 2, "not applicable (N/a)" means that the etching selectivity could not be measured.
As shown in tables 1 and 2, the etching composition for a silicon nitride layer according to the present invention can improve the etching selectivity of a silicon nitride layer with respect to a silicon oxide layer, and can prevent an increase in the thickness of the silicon oxide layer or precipitation of a silane compound by its spontaneous reaction.
In contrast, the etching composition for a silicon nitride layer of the comparative example not containing the silane compound of the present invention showed no significant improvement in etching selectivity or caused an increase in the thickness of a silicon oxide layer or precipitation of a silane compound by its spontaneous reaction.
It should be understood that various modifications, changes, alterations and equivalent embodiments can be made by those skilled in the art without departing from the spirit and scope of the invention.
Claims (4)
1. An etching composition for a silicon nitride layer, comprising:
an inorganic acid or salt thereof;
water; and
at least one of the following compounds: a compound of formula 1; a compound of formula 2; and a reaction product of the compound of formula 1 or a reaction product of the compound of formula 2:
wherein the compound of formula 1 comprises at least one of acetoxyalkyltrialkoxysilane, benzoyloxyalkyltrialkoxysilane, (alkoxycarbonyl) alkyltrialkoxysilane, and hydroxyalkyltrialkoxysilane, and
wherein the compound of formula 2 comprises at least one of glycidoxyalkyltrialkoxysilane and epoxycyclohexylalkyltrialkoxysilane.
2. The etching composition of claim 1, wherein at least one of the compound of formula 1, the compound of formula 2, and a reaction product of the compound of formula 1 or a reaction product of the compound of formula 2 is present in the etching composition for the silicon nitride layer in an amount of 0.00001 to 25 wt%.
3. The etching composition according to claim 1, wherein the inorganic acid is phosphoric acid.
4. A method for etching a semiconductor device, comprising: etching the silicon nitride layer using the etching composition for a silicon nitride layer according to any one of claims 1 to 3.
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| PCT/KR2019/007748 WO2020013485A1 (en) | 2018-07-11 | 2019-06-26 | Composition for etching silicon nitride film and method for etching silicon nitride film by using same |
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| KR20110037766A (en) * | 2009-10-07 | 2011-04-13 | 테크노세미켐 주식회사 | A composition for wet etching |
| JP2012099550A (en) * | 2010-10-29 | 2012-05-24 | Sanyo Chem Ind Ltd | Etchant for silicon nitride |
| KR20170093430A (en) * | 2016-02-05 | 2017-08-16 | 동우 화인켐 주식회사 | Etching solution composition for a silicon nitride layer and method for manufacturing a semiconductor device and a TFT array substrate using the same |
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| KR102365046B1 (en) * | 2012-12-18 | 2022-02-21 | 솔브레인 주식회사 | Composision for etching, method for etching and semiconductor device |
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| JP2012099550A (en) * | 2010-10-29 | 2012-05-24 | Sanyo Chem Ind Ltd | Etchant for silicon nitride |
| KR20170093430A (en) * | 2016-02-05 | 2017-08-16 | 동우 화인켐 주식회사 | Etching solution composition for a silicon nitride layer and method for manufacturing a semiconductor device and a TFT array substrate using the same |
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