WO2022108034A1 - Area-selective method for forming thin film using selectivity imparting agent - Google Patents
Area-selective method for forming thin film using selectivity imparting agent Download PDFInfo
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- WO2022108034A1 WO2022108034A1 PCT/KR2021/008735 KR2021008735W WO2022108034A1 WO 2022108034 A1 WO2022108034 A1 WO 2022108034A1 KR 2021008735 W KR2021008735 W KR 2021008735W WO 2022108034 A1 WO2022108034 A1 WO 2022108034A1
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- thin film
- imparting agent
- selectivity
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- chamber
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000010409 thin film Substances 0.000 title claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 238000010926 purge Methods 0.000 claims abstract description 9
- 239000000376 reactant Substances 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000010408 film Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- QUZPNFFHZPRKJD-UHFFFAOYSA-N germane Chemical compound [GeH4] QUZPNFFHZPRKJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052986 germanium hydride Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 3
- 229920005591 polysilicon Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- 239000012686 silicon precursor Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- -1 4,4-dimethylpentyl group Chemical group 0.000 description 2
- 101000735417 Homo sapiens Protein PAPPAS Proteins 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 102100034919 Protein PAPPAS Human genes 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- BIVNKSDKIFWKFA-UHFFFAOYSA-N N-propan-2-yl-N-silylpropan-2-amine Chemical compound CC(C)N([SiH3])C(C)C BIVNKSDKIFWKFA-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45534—Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
Definitions
- the present invention relates to a method for forming a thin film, and more particularly, to a method for forming a region-selective thin film using a selectivity imparting agent.
- the patterning of the semiconductor device is fabricated using an arrangement of various material layers and a lithography or etching process.
- device miniaturization has accelerated and the size of a required pattern has been reduced to the nanometer (nm) level, which greatly increases cost and time for nanopattern formation.
- various studies on a selective deposition process capable of obtaining a self-aligned structure without the need to perform a subsequent process are being conducted.
- the present invention seeks to overcome the limitations of the prior art and provide an improved method for the selective deposition of thin film materials using an ALD deposition process.
- An object of the present invention is to provide a method for forming a thin film that can be selected according to an area.
- a method for forming a region-selective thin film includes: supplying a selectivity-imparting agent into a chamber in which a substrate is placed, and adsorbing the selectivity-imparting agent to a non-growth region of the substrate; purging the interior of the chamber; a precursor supply step of supplying a precursor to the inside of the chamber and adsorbing it to the growth region of the substrate; purging the interior of the chamber; and supplying a reactant into the chamber to react with the adsorbed precursor to form a thin film.
- the method may include, prior to the step of supplying the selectivity imparting agent, contacting a wet compound with the substrate; rinsing the surface of the substrate with DI water; And it may further include the step of drying the surface of the substrate.
- the wet compound is selected from the group consisting of a composition comprising a mixture of H2O2 (28% aq), NH4OH (28-30%) and H2O, HF, Peroxide, RCA clean chemical SC-1/SC-2, H2SO4/H2O2 There may be more than one.
- the growth region may be one or more thin films selected from the group consisting of SiO2, metal oxide, copper, cobalt, tungsten, amorphous silicon, polysilicon, single crystalline silicon, germanium, and amorphous germanium hydride.
- the non-growth region may be a silicon nitride layer.
- the silicon nitride layer may be at least one selected from among SiN, SiCN, C-doped SiN, and SiON.
- the selectivity imparting agent may be represented by the following ⁇ Formula 1>.
- R1 is selected from an alkyl group having 1 to 8 carbon atoms, an aryl group, and carboxylate
- R2 is selected from hydrogen, a halogen element, and an alkyl group having 1 to 8 carbon atoms.
- the selectivity imparting agent may be represented by the following ⁇ Formula 2>.
- R is selected from hydrogen, a halogen element, an alkyl group having 1 to 8 carbon atoms, an alkyl group substituted with a halogen having 1 to 8 carbon atoms, and an aryl group having 6 to 10 carbon atoms.
- the reactant may be any one of O3, O2, and H2O.
- the precursor may be a compound containing Si.
- the subsequently supplied precursor in a state in which the selectivity imparting agent is adsorbed to the non-growth region, the subsequently supplied precursor is prevented from being adsorbed to the non-growth region, thereby preventing the formation of a thin film in the non-growth region.
- a self-aligned structure can be obtained without a subsequent process.
- FIG. 1 is a flowchart schematically illustrating a method for forming a thin film according to an embodiment of the present invention.
- FIG. 2 is a graph schematically illustrating a supply cycle according to FIG. 1 .
- FIG. 3 is a diagram schematically illustrating a process of forming a thin film according to FIG. 1 .
- FIG. 4 is a graph showing the thickness of a thin film according to an embodiment and a comparative example of the present invention.
- FIG. 5 is a table showing GPC according to an embodiment and a comparative example of the present invention.
- alkyl or “alkyl group” refers to 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 5 carbon atoms, 1 to 3 carbon atoms, straight or branched alkyl groups having from 3 to 8 carbon atoms, or from 3 to 5 carbon atoms.
- the alkyl group includes a methyl group, an ethyl group, an n-propyl group ( n Pr), an iso-propyl group ( i Pr), an n-butyl group ( n Bu), a tert-butyl group ( t Bu), an iso- Butyl group ( i Bu), sec-butyl group ( s Bu), n-pentyl group, tert-pentyl group, iso-pentyl group, sec-pentyl group, neopentyl group, 3-pentyl group, hexyl group, isohexyl group Sil group, heptyl group, 4,4-dimethylpentyl group, octyl group, 2,2,4-trimethylpentyl group, nonyl group, decyl group, undecyl group, dodecyl group, and isomers thereof, etc., but are limited thereto. it may not be
- film may include, but is not limited to, “membrane” or “thin film”.
- a film is deposited on a non-growth region, for example, an undesired region, and thus electrical characteristics and device characteristics may be deteriorated.
- the selectivity-imparting agent described below is adsorbed to the silicon nitride layer at a higher density than the silicon oxide layer, and the selectivity-imparting agent blocks the adsorption of a precursor to be introduced later to form a seed layer only on the silicon oxide layer.
- FIG. 1 is a flowchart schematically illustrating a method for forming a thin film according to an embodiment of the present invention
- FIG. 2 is a graph schematically illustrating a supply cycle according to FIG. 1
- FIG. 3 is a diagram schematically illustrating a process of forming a thin film according to FIG. 1 .
- the substrate is loaded into the process chamber, and the following ALD process conditions are adjusted.
- the ALD process conditions may include a temperature of a substrate or a process chamber, a chamber pressure, and a gas flow rate, and the temperature is 10 to 900°C.
- the substrate is exposed to a wet compound prior to the selectivity imparting agent.
- the wet compound is one selected from the group consisting of H2O2 (28% aq), NH4OH (28-30%) and a composition comprising H2O, HF, Peroxide, RCA clean chemical SC-1/SC-2, H2SO4/H2O2 mixture may be more than Thereafter, the substrate is rinsed with DI water or the like and dried.
- the substrate is exposed to the selectivity-imparting agent supplied to the interior of the chamber, and the selectivity-imparting agent is adsorbed to the surface of the non-growth region of the substrate.
- the non-growth region may be a silicon nitride layer, and may be at least one selected from among SiN, SiCN, C-doped SiN, and SiON.
- the substrate has a growth region, and the growth region may be one or more thin films selected from the group consisting of SiO2, metal oxide, copper, cobalt, tungsten, amorphous silicon, polysilicon, monocrystalline silicon, germanium and amorphous germanium hydride.
- the selectivity imparting agent is adsorbed at a high density on the surface of the non-growth region, and prevents adsorption of the precursor in a subsequent process.
- the selectivity imparting agent may be represented by the following ⁇ Formula 1>.
- R1 is selected from an alkyl group having 1 to 8 carbon atoms, an aryl group, and carboxylate
- R2 is selected from hydrogen, a halogen element, and an alkyl group having 1 to 8 carbon atoms.
- the selectivity imparting agent may be represented by the following ⁇ Formula 2>.
- R is selected from hydrogen, a halogen element, an alkyl group having 1 to 8 carbon atoms, an alkyl group substituted with a halogen having 1 to 8 carbon atoms, and an aryl group having 6 to 10 carbon atoms.
- a purge gas eg, an inert gas such as Ar
- an inert gas such as Ar
- the substrate is exposed to the precursor supplied into the chamber, and the precursor is adsorbed to the surface of the growth region and not adsorbed to the surface of the non-growth region due to the selectivity imparting agent.
- the precursor may be a compound containing Si.
- a purge gas eg, an inert gas such as Ar
- an inert gas such as Ar
- the substrate is exposed to the reactant supplied into the chamber, and a thin film is formed on the surface of the substrate.
- the reactant material reacts with the precursor layer to form a thin film, and the reactant material may be O3, O2, or H2O gas, and an oxide layer may be formed through the reactant material.
- a purge gas eg, an inert gas such as Ar
- an inert gas such as Ar
- Pretreatment was performed on SiN and SiO substrates using 1.12 wt% of DHF as a wet compound.
- the heating mantle set temperature was 100°C, and after 12 hours of dipping, it was rinsed with isopropyl alcohol and DI water. N2 blowing was performed so that no solution remained on the substrate surface.
- the silicon oxide film formation process through the ALD process is as follows, and the following process was performed as one cycle (refer to FIGS. 1 to 3).
- the silicon precursor DIPAS (Diisopropylamino Silane) is supplied to the reaction chamber and the silicon precursor is adsorbed on the substrate
- a silicon oxide layer was respectively formed on the growth region substrate (SiO) and the non-growth region substrate (SiN) without using the wet compound/selectivity imparting agent described above.
- a silicon oxide film was formed through the ALD process, the ALD process temperature was 160° C., and O3 gas was used as the reaction material.
- the silicon oxide film formation process through the ALD process is as follows, and the following process was performed as one cycle.
- the silicon precursor DIPAS is supplied to the reaction chamber and the silicon precursor is adsorbed on the substrate
- O3 gas is supplied to the reaction chamber to form a silicon oxide film
- Pretreatment was performed on SiN and SiO substrates using 1.12 wt% of DHF as a wet compound.
- the heating mantle set temperature was 100°C, and after 12 hours of dipping, it was rinsed with isopropyl alcohol and DI water. N2 blowing was performed so that no solution remained on the substrate surface. Thereafter, a silicon oxide layer was respectively formed on the growth region substrate (SiO) and the non-growth region substrate (SiN) in the same manner as in Comparative Example 1 without using a selectivity imparting agent.
- FIG. 4 is a graph showing the thickness of a thin film according to an embodiment and a comparative example of the present invention
- FIG. 5 is a table showing a GPC according to an embodiment and a comparative example of the present invention.
- the thickness decreased by 6.48% on the SiO substrate, while the thickness decreased by 89.8% on the SiN substrate, confirming that the selectivity increased.
- Such a result can be interpreted that the selectivity imparting agent adsorbed to the SiN substrate and suppressed the deposition of the silicon precursor.
- Example 1 The reason the selectivity imparting agent has selectivity in Example 1 is that it is structurally compatible with the SiN substrate to enhance the adsorption force, which is interpreted as delaying the nuclear growth of the thin film on the SiN substrate, and the desired selectivity as a result of other complex causes can get
- the present invention can be applied to various types of semiconductor manufacturing methods.
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
According to an embodiment of the present invention, an area-selective method for forming a thin film using a selectivity imparting agent comprises: a selectivity imparting agent supply step for supplying a selectivity imparting agent to the interior of a chamber in which a substrate is placed, and adsorbing the selectivity imparting agent onto a non-growth region of the substrate; a step for purging the interior of the chamber; a precursor supply step for supplying a precursor into the chamber and adsorbing the precursor onto a growth region of the substrate; a step for purging the interior of the chamber; and a thin film formation step for supplying a reactant to the interior of the chamber, and reacting the reactant with the adsorbed precursor to form a thin film.
Description
본 발명은 박막 형성 방법에 관한 것으로, 더욱 상세하게는 선택성 부여제를 이용한 영역 선택적인 박막의 형성 방법에 관한 것이다.The present invention relates to a method for forming a thin film, and more particularly, to a method for forming a region-selective thin film using a selectivity imparting agent.
반도체 소자의 패터닝은 다양한 물질층들의 배열과 리소그래피 또는 식각 공정을 이용하여 제조된다. 그러나 지난 수십년간 소자의 미세화가 가속화되었고 요구되는 패턴의 사이즈가 나노미터(nm) 수준으로 줄어 나노패턴 형성을 위해서는 비용 및 시간이 매우 증가하게 되었다. 또한, 후속 공정을 수행할 필요 없이 자체 정렬된(Self-alligned) 구조를 얻을 수 있는 선택적 증착 공정에 대한 다양한 연구가 진행되고 있다.The patterning of the semiconductor device is fabricated using an arrangement of various material layers and a lithography or etching process. However, over the past few decades, device miniaturization has accelerated and the size of a required pattern has been reduced to the nanometer (nm) level, which greatly increases cost and time for nanopattern formation. In addition, various studies on a selective deposition process capable of obtaining a self-aligned structure without the need to perform a subsequent process are being conducted.
하지만, inhibition이 불충분하거나 원하지 않는 표면 상에 후속 막이 형성되어 원하는 선택성을 얻는 것이 어렵다. 따라서, 본 발명은 종래 기술의 한계를 극복하고 ALD 증착 공정을 사용하여 박막 물질의 선택적 증착을 위한 개선된 방법을 제공하고자 한다.However, it is difficult to achieve the desired selectivity due to insufficient inhibition or subsequent film formation on the unwanted surface. Accordingly, the present invention seeks to overcome the limitations of the prior art and provide an improved method for the selective deposition of thin film materials using an ALD deposition process.
본 발명의 목적은 영역에 따른 선택이 가능한 박막 형성 방법을 제공하는 데 있다.An object of the present invention is to provide a method for forming a thin film that can be selected according to an area.
본 발명의 또 다른 목적들은 다음의 상세한 설명으로부터 보다 명확해질 것이다.Further objects of the present invention will become more apparent from the following detailed description.
본 발명의 일 실시예에 의하면, 영역 선택적 박막 형성 방법은, 선택성 부여제를 기판이 놓여진 챔버의 내부에 공급하여, 상기 기판의 비성장영역에 흡착시키는 선택성 부여제 공급 단계; 상기 챔버의 내부를 퍼지하는 단계; 상기 챔버의 내부에 전구체를 공급하여, 상기 기판의 성장영역에 흡착시키는 전구체 공급 단계; 상기 챔버의 내부를 퍼지하는 단계; 그리고 상기 챔버의 내부에 반응 물질을 공급하여 흡착된 상기 전구체와 반응하고 박막을 형성하는 박막 형성 단계를 포함한다.According to an embodiment of the present invention, a method for forming a region-selective thin film includes: supplying a selectivity-imparting agent into a chamber in which a substrate is placed, and adsorbing the selectivity-imparting agent to a non-growth region of the substrate; purging the interior of the chamber; a precursor supply step of supplying a precursor to the inside of the chamber and adsorbing it to the growth region of the substrate; purging the interior of the chamber; and supplying a reactant into the chamber to react with the adsorbed precursor to form a thin film.
상기 방법은, 상기 선택성 부여제 공급단계 이전에, 습식 화합물을 상기 기판에 접촉시키는 단계; DI water 로 상기 기판의 표면을 린스하는 단계; 그리고 상기 기판의 표면을 건조시키는 단계를 더 포함할 수 있다.The method may include, prior to the step of supplying the selectivity imparting agent, contacting a wet compound with the substrate; rinsing the surface of the substrate with DI water; And it may further include the step of drying the surface of the substrate.
상기 습식 화합물은, H2O2(28% aq), NH4OH(28~30%) 와 H2O, HF, Peroxide, RCA clean chemical SC-1/SC-2, H2SO4/H2O2 혼합물을 포함하는 조성물로 구성된 군에서 선택된 하나 이상일 수 있다.The wet compound is selected from the group consisting of a composition comprising a mixture of H2O2 (28% aq), NH4OH (28-30%) and H2O, HF, Peroxide, RCA clean chemical SC-1/SC-2, H2SO4/H2O2 There may be more than one.
상기 성장영역은 SiO2, 금속 산화물, 동, 코발트, 텅스텐, 비정질 실리콘, 폴리실리콘, 단결정성 실리콘, 게르마늄과 비정질 수소화 게르마늄으로 구성된 군에서 선택된 하나 이상의 박막일 수 있다.The growth region may be one or more thin films selected from the group consisting of SiO2, metal oxide, copper, cobalt, tungsten, amorphous silicon, polysilicon, single crystalline silicon, germanium, and amorphous germanium hydride.
상기 비성장영역은 실리콘 질화막일 수 있다.The non-growth region may be a silicon nitride layer.
상기 실리콘 질화막은 SiN, SiCN, C-doped SiN, SiON 중 선택된 하나 이상일 수 있다.The silicon nitride layer may be at least one selected from among SiN, SiCN, C-doped SiN, and SiON.
상기 선택성 부여제는 하기 <화학식 1>로 표시될 수 있다.The selectivity imparting agent may be represented by the following <Formula 1>.
<화학식 1><Formula 1>
상기 <화학식 1>에서, R1은 탄소 개수가 1 내지 8인 알킬기, 아릴기, 카르복실레이트 중에서 선택되며, R2는 수소, 할로젠 원소, 탄소 개수가 1 내지 8인 알킬기 중에서 선택된다.In <Formula 1>, R1 is selected from an alkyl group having 1 to 8 carbon atoms, an aryl group, and carboxylate, and R2 is selected from hydrogen, a halogen element, and an alkyl group having 1 to 8 carbon atoms.
상기 선택성 부여제는 하기 <화학식 2>로 표시될 수 있다.The selectivity imparting agent may be represented by the following <Formula 2>.
<화학식 2><Formula 2>
상기 <화학식 2>에서, R은 수소, 할로젠 원소, 탄소수 1 내지 8인 알킬기, 탄소수 1 내지 8의 할로젠으로 치환된 알킬기, 탄소수 6 내지 10의 아릴기 중에서 선택된다.In <Formula 2>, R is selected from hydrogen, a halogen element, an alkyl group having 1 to 8 carbon atoms, an alkyl group substituted with a halogen having 1 to 8 carbon atoms, and an aryl group having 6 to 10 carbon atoms.
상기 반응 물질은 O3, O2, H2O 중 어느 하나일 수 있다.The reactant may be any one of O3, O2, and H2O.
상기 전구체는 Si 을 포함하는 화합물일 수 있다.The precursor may be a compound containing Si.
본 발명의 일 실시예에 의하면, 선택성 부여제가 비성장영역에 흡착된 상태에서 후속적으로 공급되는 전구체가 비성장영역에 흡착되는 것을 방지하며, 이를 통해 비성장영역에 박막이 형성되는 것을 방지할 수 있다. 또한, 이를 통해 후속 공정 없이도 자체 정렬된 구조를 얻을 수 있다.According to an embodiment of the present invention, in a state in which the selectivity imparting agent is adsorbed to the non-growth region, the subsequently supplied precursor is prevented from being adsorbed to the non-growth region, thereby preventing the formation of a thin film in the non-growth region. can In addition, through this, a self-aligned structure can be obtained without a subsequent process.
도 1은 본 발명의 일 실시예에 따른 박막 형성 방법을 개략적으로 나타내는 흐름도이다.1 is a flowchart schematically illustrating a method for forming a thin film according to an embodiment of the present invention.
도 2는 도 1에 따른 공급 주기를 개략적으로 나타내는 그래프이다.FIG. 2 is a graph schematically illustrating a supply cycle according to FIG. 1 .
도 3은 도 1에 따른 박막 형성 과정을 개략적으로 나타내는 도면이다.FIG. 3 is a diagram schematically illustrating a process of forming a thin film according to FIG. 1 .
도 4는 본 발명의 일 실시예 및 비교예에 따른 박막의 두께를 나타내는 그래프이다.4 is a graph showing the thickness of a thin film according to an embodiment and a comparative example of the present invention.
도 5는 본 발명의 일 실시예 및 비교예에 따른 GPC를 나타내는 표이다.5 is a table showing GPC according to an embodiment and a comparative example of the present invention.
이하, 본 발명의 바람직한 실시예들을 첨부된 도 1 내지 도 5를 참고하여 더욱 상세히 설명한다. 본 발명의 실시예들은 여러 가지 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 설명하는 실시예들에 한정되는 것으로 해석되어서는 안 된다. 본 실시예들은 당해 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 본 발명을 더욱 상세하게 설명하기 위해서 제공되는 것이다. 따라서 도면에 나타난 각 요소의 형상은 보다 분명한 설명을 강조하기 위하여 과장될 수 있다.Hereinafter, preferred embodiments of the present invention will be described in more detail with reference to the accompanying drawings 1 to 5. Embodiments of the present invention may be modified in various forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. These examples are provided to explain the present invention in more detail to those of ordinary skill in the art to which the present invention pertains. Accordingly, the shape of each element shown in the drawings may be exaggerated to emphasize a clearer description.
본원 명세서 전체에서, 어떤 부분이 어떤 구성 요소를 "포함"한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성 요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다.Throughout this specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.
본원 명세서 전체에서 사용되는 정도의 용어 "약", "실질적으로" 등은 언급된 의미에 고유한 제조 및 물질 허용 오차가 제시될 때 그 수치에서 또는 그 수치에 근접한 의미로 사용되고, 본원의 이해를 돕기 위해 정확하거나 절대적인 수치가 언급된 개시 내용을 비양심적인 침해자가 부당하게 이용하는 것을 방지하기 위해 사용된다.As used throughout this specification, the terms "about," "substantially," and the like are used in a sense at or close to the numerical value when the manufacturing and material tolerances inherent in the stated meaning are presented, and are intended to enhance the understanding of this application. To help, precise or absolute figures are used to prevent unfair use by unconscionable infringers of the stated disclosure.
본원 명세서 전체에서, 용어 "알킬"또는 "알킬기"는, 1 내지 12 개의 탄소 원자, 1 내지 10 개의 탄소 원자, 1 내지 8 개의 탄소 원자, 1 내지 5 개의 탄소 원자, 1 내지 3 개의 탄소 원자, 3 내지 8 개의 탄소 원자, 또는 3 내지 5 개의 탄소 원자를 갖는 선형 또는 분지형 알킬기를 포함한다. 예를 들어, 상기 알킬기로는 메틸기, 에틸기, n-프로필기(nPr), iso-프로필기(iPr), n-부틸기(nBu), tert-부틸기(tBu), iso-부틸기(iBu), sec-부틸기(sBu), n-펜틸기, tert-펜틸기, iso-펜틸기, sec-펜틸기, 네오펜틸기, 3-펜틸기, 헥실기, 이소헥실기, 헵틸기, 4,4-디메틸펜틸기, 옥틸기, 2,2,4-트리메틸펜틸기, 노닐기, 데실기, 운데실기, 도데실기, 및 이들의 이성질체 등을 들 수 있으나, 이에 제한되지 않을 수 있다.Throughout this specification, the term "alkyl" or "alkyl group" refers to 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 5 carbon atoms, 1 to 3 carbon atoms, straight or branched alkyl groups having from 3 to 8 carbon atoms, or from 3 to 5 carbon atoms. For example, the alkyl group includes a methyl group, an ethyl group, an n-propyl group ( n Pr), an iso-propyl group ( i Pr), an n-butyl group ( n Bu), a tert-butyl group ( t Bu), an iso- Butyl group ( i Bu), sec-butyl group ( s Bu), n-pentyl group, tert-pentyl group, iso-pentyl group, sec-pentyl group, neopentyl group, 3-pentyl group, hexyl group, isohexyl group Sil group, heptyl group, 4,4-dimethylpentyl group, octyl group, 2,2,4-trimethylpentyl group, nonyl group, decyl group, undecyl group, dodecyl group, and isomers thereof, etc., but are limited thereto. it may not be
본원 명세서 전체에서, 용어 "막"은 "막" 또는 "박막"을 포함하는 것일 수 있으나, 이에 제한되지 않을 수 있다.Throughout this specification, the term “film” may include, but is not limited to, “membrane” or “thin film”.
종래의 공정은 비성장영역, 예를 들어 원하지 않는 영역에 막이 쌓이게 되어 전기적 특성 및 소자 특성이 열화될 수 있다. 그러나, 이하에서 설명하는 선택성 부여제는 실리콘 산화막 보다 실리콘 질화막에 더 높은 밀도로 흡착되며, 선택성 부여제는 이후에 투입되는 전구체의 흡착을 막아 실리콘 산화막에만 seed layer를 형성할 수 있다.In the conventional process, a film is deposited on a non-growth region, for example, an undesired region, and thus electrical characteristics and device characteristics may be deteriorated. However, the selectivity-imparting agent described below is adsorbed to the silicon nitride layer at a higher density than the silicon oxide layer, and the selectivity-imparting agent blocks the adsorption of a precursor to be introduced later to form a seed layer only on the silicon oxide layer.
도 1은 본 발명의 일 실시예에 따른 박막 형성 방법을 개략적으로 나타내는 흐름도이며, 도 2는 도 1에 따른 공급 주기를 개략적으로 나타내는 그래프이다. 도 3은 도 1에 따른 박막 형성 과정을 개략적으로 나타내는 도면이다.1 is a flowchart schematically illustrating a method for forming a thin film according to an embodiment of the present invention, and FIG. 2 is a graph schematically illustrating a supply cycle according to FIG. 1 . FIG. 3 is a diagram schematically illustrating a process of forming a thin film according to FIG. 1 .
기판은 공정챔버의 내부로 로드되며, 이하의 ALD 공정 조건은 조정된다. ALD 공정 조건은 기판 또는 공정챔버의 온도, 챔버 압력, 가스 유동률을 포함할 수 있으며, 온도는 10 내지 900℃이다.The substrate is loaded into the process chamber, and the following ALD process conditions are adjusted. The ALD process conditions may include a temperature of a substrate or a process chamber, a chamber pressure, and a gas flow rate, and the temperature is 10 to 900°C.
먼저, 기판은 선택성 부여제 이전에 습식 화합물에 노출된다. 습식 화합물은, H2O2(28% aq), NH4OH(28~30%) 와 H2O, HF, Peroxide, RCA clean chemical SC-1/SC-2, H2SO4/H2O2 혼합물을 포함하는 조성물로 구성된 군에서 선택된 하나 이상일 수 있다. 이후, 기판은 DI water 등으로 린스 처리된 후 건조된다.First, the substrate is exposed to a wet compound prior to the selectivity imparting agent. The wet compound is one selected from the group consisting of H2O2 (28% aq), NH4OH (28-30%) and a composition comprising H2O, HF, Peroxide, RCA clean chemical SC-1/SC-2, H2SO4/H2O2 mixture may be more than Thereafter, the substrate is rinsed with DI water or the like and dried.
다음으로, 기판은 챔버의 내부에 공급된 선택성 부여제에 노출되며, 선택성 부여제는 기판의 비성장영역 표면에 흡착된다. 비성장영역은 실리콘 질화막일 수 있으며, SiN, SiCN, C-doped SiN, SiON 중 선택된 하나 이상일 수 있다. 또한, 기판은 성장영역을 가지며, 성장영역은 SiO2, 금속 산화물, 동, 코발트, 텅스텐, 비정질 실리콘, 폴리실리콘, 단결정성 실리콘, 게르마늄과 비정질 수소화 게르마늄으로 구성된 군에서 선택된 하나 이상의 박막일 수 있다. 선택성 부여제는 비성장영역의 표면에 높은 밀도로 흡착되며, 후속 공정에서 전구체가 흡착되는 것을 방해한다.Next, the substrate is exposed to the selectivity-imparting agent supplied to the interior of the chamber, and the selectivity-imparting agent is adsorbed to the surface of the non-growth region of the substrate. The non-growth region may be a silicon nitride layer, and may be at least one selected from among SiN, SiCN, C-doped SiN, and SiON. In addition, the substrate has a growth region, and the growth region may be one or more thin films selected from the group consisting of SiO2, metal oxide, copper, cobalt, tungsten, amorphous silicon, polysilicon, monocrystalline silicon, germanium and amorphous germanium hydride. The selectivity imparting agent is adsorbed at a high density on the surface of the non-growth region, and prevents adsorption of the precursor in a subsequent process.
선택성 부여제는 하기 <화학식 1>로 표시될 수 있다.The selectivity imparting agent may be represented by the following <Formula 1>.
<화학식 1><Formula 1>
상기 <화학식 1>에서, R1은 탄소 개수가 1 내지 8인 알킬기, 아릴기, 카르복실레이트 중에서 선택되며, R2는 수소, 할로젠 원소, 탄소 개수가 1 내지 8인 알킬기 중에서 선택된다.In <Formula 1>, R1 is selected from an alkyl group having 1 to 8 carbon atoms, an aryl group, and carboxylate, and R2 is selected from hydrogen, a halogen element, and an alkyl group having 1 to 8 carbon atoms.
선택성 부여제는 하기 <화학식 2>로 표시될 수 있다.The selectivity imparting agent may be represented by the following <Formula 2>.
<화학식 2><Formula 2>
상기 <화학식 2>에서, R은 수소, 할로젠 원소, 탄소수 1 내지 8인 알킬기, 탄소수 1 내지 8의 할로젠으로 치환된 알킬기, 탄소수 6 내지 10의 아릴기 중에서 선택된다.In <Formula 2>, R is selected from hydrogen, a halogen element, an alkyl group having 1 to 8 carbon atoms, an alkyl group substituted with a halogen having 1 to 8 carbon atoms, and an aryl group having 6 to 10 carbon atoms.
이후, 챔버의 내부에 퍼지가스(예를 들어, Ar과 같은 비활성가스)를 공급하여, 미흡착 선택성 부여제 또는 부산물을 제거하거나 정화한다.Thereafter, a purge gas (eg, an inert gas such as Ar) is supplied to the inside of the chamber to remove or purify the non-adsorbed selectivity-imparting agent or by-product.
이후, 기판은 챔버의 내부에 공급된 전구체에 노출되며, 전구체는 성장영역의 표면에 흡착되고 비성장영역의 표면에는 선택성 부여제로 인해 흡착되지 않는다. 전구체는 Si 을 포함하는 화합물일 수 있다.Thereafter, the substrate is exposed to the precursor supplied into the chamber, and the precursor is adsorbed to the surface of the growth region and not adsorbed to the surface of the non-growth region due to the selectivity imparting agent. The precursor may be a compound containing Si.
이후, 챔버의 내부에 퍼지가스(예를 들어, Ar과 같은 비활성가스)를 공급하여, 미흡착 전구체 또는 부산물을 제거하거나 정화한다.Thereafter, a purge gas (eg, an inert gas such as Ar) is supplied to the inside of the chamber to remove or purify unadsorbed precursors or by-products.
이후, 기판은 챔버의 내부에 공급된 반응 물질에 노출되며, 기판의 표면에 박막이 형성된다. 반응 물질은 전구체층과 반응하여 박막을 형성하며, 반응 물질은 O3, O2, H2O 가스 일 수 있고 반응 물질을 통해 산화막이 형성될 수 있다.Thereafter, the substrate is exposed to the reactant supplied into the chamber, and a thin film is formed on the surface of the substrate. The reactant material reacts with the precursor layer to form a thin film, and the reactant material may be O3, O2, or H2O gas, and an oxide layer may be formed through the reactant material.
이후, 챔버의 내부에 퍼지가스(예를 들어, Ar과 같은 비활성가스)를 공급하여, 미반응 물질 또는 부산물을 제거하거나 정화한다.Thereafter, a purge gas (eg, an inert gas such as Ar) is supplied to the inside of the chamber to remove or purify unreacted materials or by-products.
- 실시예 1- Example 1
습식 화합물로 DHF 1.12wt% 사용하여 SiN, SiO 기판에 대한 전처리를 진행하였다. Heating mantle 설정온도는 100℃ 이고, 12시간 Dipping 후 이소프로필알콜, DI Water로 린스하였다. 기판 표면에 용액이 남지 않도록 N2 Blowing을 진행하였다. Pretreatment was performed on SiN and SiO substrates using 1.12 wt% of DHF as a wet compound. The heating mantle set temperature was 100℃, and after 12 hours of dipping, it was rinsed with isopropyl alcohol and DI water. N2 blowing was performed so that no solution remained on the substrate surface.
앞서 설명한 선택성 부여제인 Propionaldehyde를 성장영역기판(SiO) 및 비성장영역기판(SiN) 상에 각각 공급한 후 실리콘 산화막을 형성하였다. ALD 공정을 통해 실리콘 산화막을 형성하였으며, ALD 공정 온도는 160℃, 반응 물질은 O3 가스를 사용하였다.After the above-described selectivity imparting agent, propionaldehyde, was supplied on the growth region substrate (SiO) and the non-growth region substrate (SiN), respectively, a silicon oxide layer was formed. A silicon oxide film was formed through the ALD process, the ALD process temperature was 160° C., and O3 gas was used as the reaction material.
ALD 공정을 통한 실리콘 산화막 형성 과정은 아래와 같으며, 아래 과정을 1사이클로 하여 진행하였다(도 1 내지 3 참고).The silicon oxide film formation process through the ALD process is as follows, and the following process was performed as one cycle (refer to FIGS. 1 to 3).
1) 반응 챔버 내에 선택성 부여제를 공급하여 기판에 흡착1) Adsorbed to the substrate by supplying a selectivity-imparting agent in the reaction chamber
2) 반응 챔버 내에 Ar 가스를 공급하여 미흡착 선택성 부여제 또는 부산물을 제거2) Removal of non-adsorbed selectivity-imparting agents or by-products by supplying Ar gas into the reaction chamber
3) Ar을 캐리어 가스로 하여, 실리콘 전구체 DIPAS(Diisopropylamino Silane)를 반응 챔버에 공급하고 기판에 실리콘 전구체를 흡착3) Using Ar as a carrier gas, the silicon precursor DIPAS (Diisopropylamino Silane) is supplied to the reaction chamber and the silicon precursor is adsorbed on the substrate
4) 반응 챔버 내에 Ar 가스를 공급하여 미흡착 실리콘 전구체 또는 부산물을 제거4) Removal of unadsorbed silicon precursors or by-products by supplying Ar gas into the reaction chamber
5) O3 가스를 반응 챔버에 공급하여 실리콘 산화막을 형성5) O3 gas is supplied to the reaction chamber to form a silicon oxide film
6) 반응 챔버 내에 Ar 가스를 공급하여 미반응물질 또는 부산물을 제거6) Removal of unreacted substances or by-products by supplying Ar gas into the reaction chamber
- 비교예 1- Comparative Example 1
앞서 설명한 습식화합물/선택성 부여제를 사용하지 않고 성장영역기판(SiO) 및 비성장영역기판(SiN) 상에 각각 실리콘 산화막을 형성하였다. ALD 공정을 통해 실리콘 산화막을 형성하였으며, ALD 공정 온도는 160℃, 반응 물질은 O3 가스를 사용하였다.A silicon oxide layer was respectively formed on the growth region substrate (SiO) and the non-growth region substrate (SiN) without using the wet compound/selectivity imparting agent described above. A silicon oxide film was formed through the ALD process, the ALD process temperature was 160° C., and O3 gas was used as the reaction material.
ALD 공정을 통한 실리콘 산화막 형성 과정은 아래와 같으며, 아래 과정을 1사이클로 하여 진행하였다.The silicon oxide film formation process through the ALD process is as follows, and the following process was performed as one cycle.
1) Ar을 캐리어 가스로 하여, 실리콘 전구체 DIPAS를 반응 챔버에 공급하고 기판에 실리콘 전구체를 흡착1) Using Ar as a carrier gas, the silicon precursor DIPAS is supplied to the reaction chamber and the silicon precursor is adsorbed on the substrate
2) 반응 챔버 내에 Ar 가스를 공급하여 미흡착 실리콘 전구체 또는 부산물을 제거2) Removal of unadsorbed silicon precursors or by-products by supplying Ar gas into the reaction chamber
3) O3 가스를 반응 챔버에 공급하여 실리콘 산화막을 형성3) O3 gas is supplied to the reaction chamber to form a silicon oxide film
4) 반응 챔버 내에 Ar 가스를 공급하여 미반응물질 또는 부산물을 제거4) Removal of unreacted substances or by-products by supplying Ar gas into the reaction chamber
- 비교예 2- Comparative Example 2
습식 화합물로 DHF 1.12wt% 사용하여 SiN, SiO 기판에 대한 전처리를 진행하였다. Heating mantle 설정온도는 100℃ 이고, 12시간 Dipping 후 이소프로필알콜, DI Water로 린스하였다. 기판 표면에 용액이 남지 않도록 N2 Blowing을 진행하였다. 이후 선택성 부여제를 사용하지 않고, 비교예 1과 동일한 방법으로 성장영역기판(SiO) 및 비성장영역기판(SiN) 상에 각각 실리콘 산화막을 형성하였다.Pretreatment was performed on SiN and SiO substrates using 1.12 wt% of DHF as a wet compound. The heating mantle set temperature was 100℃, and after 12 hours of dipping, it was rinsed with isopropyl alcohol and DI water. N2 blowing was performed so that no solution remained on the substrate surface. Thereafter, a silicon oxide layer was respectively formed on the growth region substrate (SiO) and the non-growth region substrate (SiN) in the same manner as in Comparative Example 1 without using a selectivity imparting agent.
도 4는 본 발명의 일 실시예 및 비교예에 따른 박막의 두께를 나타내는 그래프이며, 도 5는 본 발명의 일 실시예 및 비교예에 따른 GPC를 나타내는 표이다. 비교예 1에서의 SiO 두께(A)는 SiN기판 : SiO기판 = 69.97 : 60.44, 비교예 2에서의 SiO 두께(A)는 SiN기판 : SiO기판 = 62.48 : 62.47 인 반면, 실시예 1에서는 SiN기판 : SiO기판 = 6.36 : 58.42 로 선택성이 증가했다.4 is a graph showing the thickness of a thin film according to an embodiment and a comparative example of the present invention, and FIG. 5 is a table showing a GPC according to an embodiment and a comparative example of the present invention. The SiO thickness (A) in Comparative Example 1 was SiN substrate: SiO substrate = 69.97: 60.44, and the SiO thickness (A) in Comparative Example 2 was SiN substrate: SiO substrate = 62.48: 62.47, whereas in Example 1, SiN substrate : SiO substrate = 6.36: 58.42, the selectivity increased.
SiO 기판에서 두께가 6.48% 감소한 반면, SiN 기판에서 두께가 89.8% 감소하였으며, 선택성이 증가한 것을 확인할 수 있다. 이와 같은 결과는 선택성 부여제가 SiN 기판에 흡착하여 실리콘 전구체 증착을 억제한 것으로 해석할 수 있다.The thickness decreased by 6.48% on the SiO substrate, while the thickness decreased by 89.8% on the SiN substrate, confirming that the selectivity increased. Such a result can be interpreted that the selectivity imparting agent adsorbed to the SiN substrate and suppressed the deposition of the silicon precursor.
실시예 1에서 선택성 부여제가 선택성을 가지는 이유는 SiN 기판과 구조적으로 적합하여 흡착력이 강화되고, 이로 인해 SiN 기판에서 박막의 핵 성장을 지연시키는 것으로 해석되며, 기타 복합적인 원인에 의한 결과로 원하는 선택성을 얻을 수 있다.The reason the selectivity imparting agent has selectivity in Example 1 is that it is structurally compatible with the SiN substrate to enhance the adsorption force, which is interpreted as delaying the nuclear growth of the thin film on the SiN substrate, and the desired selectivity as a result of other complex causes can get
이상에서 본 발명을 실시예를 통하여 상세하게 설명하였으나, 이와 다른 형태의 실시예들도 가능하다. 그러므로, 이하에 기재된 청구항들의 기술적 사상과 범위는 실시예들에 한정되지 않는다.Although the present invention has been described in detail through examples above, other types of embodiments are also possible. Therefore, the spirit and scope of the claims set forth below are not limited to the embodiments.
본 발명은 다양한 형태의 반도체 제조방법에 응용될 수 있다.The present invention can be applied to various types of semiconductor manufacturing methods.
Claims (10)
- 선택성 부여제를 기판이 놓여진 챔버의 내부에 공급하여, 상기 기판의 비성장영역에 흡착시키는 선택성 부여제 공급 단계;a selectivity-imparting agent supplying step of supplying a selectivity-imparting agent to the inside of the chamber in which the substrate is placed and adsorbing the selectivity-imparting agent to the non-growth region of the substrate;상기 챔버의 내부를 퍼지하는 단계;purging the interior of the chamber;상기 챔버의 내부에 전구체를 공급하여, 상기 기판의 성장영역에 흡착시키는 전구체 공급 단계;a precursor supply step of supplying a precursor to the inside of the chamber and adsorbing it to the growth region of the substrate;상기 챔버의 내부를 퍼지하는 단계; 및purging the interior of the chamber; and상기 챔버의 내부에 반응 물질을 공급하여 흡착된 상기 전구체와 반응하고 박막을 형성하는 박막 형성 단계를 포함하는, 영역 선택적 박막 형성 방법.and a thin film forming step of supplying a reactant into the chamber to react with the adsorbed precursor to form a thin film.
- 제1항에 있어서,According to claim 1,상기 방법은,The method is상기 선택성 부여제 공급단계 이전에, 습식 화합물을 상기 기판에 접촉시키는 단계를 더 포함하는, 영역 선택적 박막 형성 방법.prior to the step of supplying the selectivity imparting agent, the method further comprising the step of contacting a wet compound to the substrate.
- 제2항에 있어서,3. The method of claim 2,상기 습식 화합물은,The wet compound isH2O2(28% aq), NH4OH(28~30%) 와 H2O, HF, Peroxide, RCA clean chemical SC-1/SC-2, H2SO4/H2O2 혼합물을 포함하는 조성물로 구성된 군에서 선택된 하나 이상인, 영역 선택적 박막 형성 방법.At least one selected from the group consisting of H2O2 (28% aq), NH4OH (28-30%) and a composition comprising a mixture of H2O, HF, Peroxide, RCA clean chemical SC-1/SC-2, H2SO4/H2O2, area selective A method of forming a thin film.
- 제1항에 있어서,According to claim 1,상기 성장영역은 SiO2, 금속 산화물, 동, 코발트, 텅스텐, 비정질 실리콘, 폴리실리콘, 단결정성 실리콘, 게르마늄과 비정질 수소화 게르마늄으로 구성된 군에서 선택된 하나 이상의 박막인, 영역 선택적 박막 형성 방법.The growth region is at least one thin film selected from the group consisting of SiO2, metal oxide, copper, cobalt, tungsten, amorphous silicon, polysilicon, monocrystalline silicon, germanium and amorphous germanium hydride.
- 제1항에 있어서, According to claim 1,상기 비성장영역은 실리콘 질화막인, 영역 선택적 박막 형성 방법.wherein the non-growth region is a silicon nitride film.
- 제5항에 있어서,6. The method of claim 5,상기 실리콘 질화막은 SiN, SiCN, C-doped SiN, SiON 중 선택된 하나 이상인, 영역 선택적 박막 형성 방법.The silicon nitride film is at least one selected from SiN, SiCN, C-doped SiN, and SiON.
- 제1항에 있어서,According to claim 1,상기 선택성 부여제는 하기 <화학식 1>로 표시되는, 영역 선택적 박막 형성 방법.The method for forming a region-selective thin film, wherein the selectivity imparting agent is represented by the following <Formula 1>.<화학식 1><Formula 1>
상기 <화학식 1>에서, R1은 탄소 개수가 1 내지 8인 알킬기, 아릴기, 카르복실레이트 중에서 선택되며, R2는 수소, 할로젠 원소, 탄소 개수가 1 내지 8인 알킬기 중에서 선택된다.In <Formula 1>, R1 is selected from an alkyl group having 1 to 8 carbon atoms, an aryl group, and carboxylate, and R2 is selected from hydrogen, a halogen element, and an alkyl group having 1 to 8 carbon atoms. - 제1항에 있어서,According to claim 1,상기 선택성 부여제는 하기 <화학식 2>로 표시되는, 영역 선택적 박막 형성 방법.The method for forming a region-selective thin film, wherein the selectivity imparting agent is represented by the following <Formula 2>.<화학식 2><Formula 2>
상기 <화학식 2>에서, R은 수소, 할로젠 원소, 탄소수 1 내지 8인 알킬기, 탄소수 1 내지 8의 할로젠으로 치환된 알킬기, 탄소수 6 내지 10의 아릴기 중에서 선택된다.In <Formula 2>, R is selected from hydrogen, a halogen element, an alkyl group having 1 to 8 carbon atoms, an alkyl group substituted with a halogen having 1 to 8 carbon atoms, and an aryl group having 6 to 10 carbon atoms. - 제1항에 있어서,According to claim 1,상기 반응 물질은 O3, O2, H2O 중 어느 하나인, 영역 선택적 박막 형성 방법.The reactive material is any one of O3, O2, and H2O.
- 제1항에 있어서,According to claim 1,상기 전구체는 Si 을 포함하는 화합물인, 영역 선택적 박막 형성 방법.The precursor is a compound containing Si, a method for forming a region-selective thin film.
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| WO2019071215A1 (en) * | 2017-10-06 | 2019-04-11 | Applied Materials, Inc. | Methods and precursors for selective deposition of metal films |
| WO2020046746A1 (en) * | 2018-08-27 | 2020-03-05 | Versum Materials Us, Llc | Selective deposition on silicon containing surfaces |
| KR20200108243A (en) * | 2019-03-08 | 2020-09-17 | 에이에스엠 아이피 홀딩 비.브이. | Structure Including SiOC Layer and Method of Forming Same |
| KR102095710B1 (en) * | 2019-11-05 | 2020-04-01 | 주식회사 유진테크 머티리얼즈 | Method of depositing thin films using protective material |
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| Publication number | Publication date |
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| KR102504146B1 (en) | 2023-02-27 |
| KR20220070795A (en) | 2022-05-31 |
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