CN117026207A - Aluminum precursor and method for manufacturing the same, thin layer and method for manufacturing memory device - Google Patents
Aluminum precursor and method for manufacturing the same, thin layer and method for manufacturing memory device Download PDFInfo
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- CN117026207A CN117026207A CN202310526085.6A CN202310526085A CN117026207A CN 117026207 A CN117026207 A CN 117026207A CN 202310526085 A CN202310526085 A CN 202310526085A CN 117026207 A CN117026207 A CN 117026207A
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- 239000002243 precursor Substances 0.000 title claims abstract description 149
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 55
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 61
- 239000000126 substance Substances 0.000 claims abstract description 135
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 93
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 33
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 21
- 125000003118 aryl group Chemical group 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 125000003277 amino group Chemical group 0.000 claims abstract description 10
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 10
- 125000005265 dialkylamine group Chemical group 0.000 claims abstract description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract description 9
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 32
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- IOPLHGOSNCJOOO-UHFFFAOYSA-N methyl 3,4-diaminobenzoate Chemical compound COC(=O)C1=CC=C(N)C(N)=C1 IOPLHGOSNCJOOO-UHFFFAOYSA-N 0.000 claims description 12
- ZERULLAPCVRMCO-UHFFFAOYSA-N sulfure de di n-propyle Natural products CCCSCCC ZERULLAPCVRMCO-UHFFFAOYSA-N 0.000 claims description 12
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 claims description 10
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 6
- COOGPNLGKIHLSK-UHFFFAOYSA-N aluminium sulfide Chemical compound [Al+3].[Al+3].[S-2].[S-2].[S-2] COOGPNLGKIHLSK-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000010408 film Substances 0.000 description 49
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 38
- 239000010410 layer Substances 0.000 description 37
- 230000008569 process Effects 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 208000034841 Thrombotic Microangiopathies Diseases 0.000 description 17
- 238000000151 deposition Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 230000008021 deposition Effects 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 238000003860 storage Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- 230000009257 reactivity Effects 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000002411 thermogravimetry Methods 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000000113 differential scanning calorimetry Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 4
- 230000006399 behavior Effects 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 4
- 230000008016 vaporization Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- WXEHBUMAEPOYKP-UHFFFAOYSA-N methylsulfanylethane Chemical group CCSC WXEHBUMAEPOYKP-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- 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]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
-
- 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
- C23C16/403—Oxides of aluminium, magnesium or beryllium
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
A method for producing an aluminum precursor by mixing 1 to 3 moles of a compound represented by the following chemical formula 1 or the following chemical formula 2 and 1 to 3 moles of a compound represented by the following chemical formula 3,<chemical formula 1>X is O or S, R1 or R2 are each independently selected from alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 12 carbon atoms,<chemical formula 2>X is O or S, n is 1 to 5, R1 to R4 are each independently selected from a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms and an aryl group of 6 to 12 carbon atoms,<chemical formula 3>R1, R2 and R3 are different from each other and are each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a dialkylamine having 1 to 6 carbon atoms, a cyclic amine group having 1 to 6 carbon atoms or a halogen atom.
Description
Technical Field
The present invention relates to an aluminum precursor, a method of forming a thin layer using the aluminum precursor, a method of manufacturing the aluminum precursor, and a method of manufacturing a storage device, and more particularly, to an aluminum precursor having excellent safety, easy control of a thin layer thickness, and excellent step coverage characteristics, a method of forming a thin layer using the aluminum precursor, a method of manufacturing the aluminum precursor, and a method of manufacturing a storage device.
Background
The existing 2D NAND flash memory process shows technical limitations of interference and leakage emphasis between cells when the integration level increases in a small area. To overcome this disadvantage, a 3D NAND flash process of vertically stacking cells has emerged.
Advantages of the 3D NAND flash memory including the multi-layer stack include: the interference between the cells is rapidly reduced to improve characteristics, and by increasing the above-described stack, data capacity is increased and cost is reduced. As a result, compared with the conventional NAND memory device, it has a write speed of more than two times, a endurance of more than 10 times, and power consumption is half.
However, with the ultra-high stack having a height increased to 90 layers or more, it is more difficult to secure a uniform thin film on the sidewall, and a limitation occurs that a characteristic difference is generated between the uppermost cell and the lowermost cell. Accordingly, there is an increasing demand for a method of manufacturing a uniform thickness thin film capable of forming a three-dimensional structure having a large aspect ratio with excellent step coverage.
In addition, aluminum-containing films play a very important role in the manufacture of semiconductor devices. The aluminum-containing film includes: aluminum films, aluminum nitride films, aluminum carbonitride films, aluminum oxide films, aluminum oxynitride films, and the like, which serve as important roles of passivation layers, interlayer insulating films, capacitor dielectric layers, and the like.
Currently, trimethylaluminum (TMA) or triisobutylaluminum is used as a precursor for depositing aluminum-containing films, but these materials are explosively flammable and require much attention for disposal.
Disclosure of Invention
An object of the present invention is to provide an aluminum precursor having excellent vaporization characteristics and thermal stability, a method of forming a thin film using the aluminum precursor, a method of manufacturing the aluminum precursor, and a method of manufacturing a storage device.
Another object of the present invention is to provide an aluminum precursor having excellent step coverage, a method of forming a thin film using the aluminum precursor, a method of manufacturing the aluminum precursor, and a method of manufacturing a storage device.
Another object of the present invention is to provide an aluminum precursor capable of forming a thin film having a very uniform thickness and easily controlled thickness, a method of forming a thin film using the aluminum precursor, a method of manufacturing an aluminum precursor, and a method of manufacturing a storage device.
Other objects of the present invention will become more apparent in the detailed description that follows.
Disclosed is a method for producing an aluminum precursor, wherein 1-3 moles of a compound represented by the following chemical formula 1 or the following chemical formula 2 and 1-3 moles of a compound represented by the following chemical formula 3 are mixed to form the aluminum precursor.
< chemical formula 1>
Wherein X is O or S, and R1 or R2 are each independently selected from alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 12 carbon atoms.
< chemical formula 2>
Wherein X is O or S, n is 1 to 5, and R1 to R4 are each independently selected from a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.
< chemical formula 3>
Wherein R1, R2 and R3 are different from each other and are each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a dialkylamine having 1 to 6 carbon atoms, a cyclic amine group having 1 to 6 carbon atoms or a halogen atom.
The aluminum precursor may be formed by mixing ethyl methyl sulfide and trimethylaluminum.
The aluminum precursor may be formed by mixing ethyl propyl ether and trimethylaluminum.
Disclosed is an aluminum precursor, which is formed by mixing 1 to 3 moles of a compound represented by the following chemical formula 1 or the following chemical formula 2 and 1 to 3 moles of a compound represented by the following chemical formula 3.
< chemical formula 1>
Wherein X is O or S, and R1 or R2 are each independently selected from alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 12 carbon atoms.
< chemical formula 2>
Wherein X is O or S, n is 1 to 5, and R1 to R4 are each independently selected from a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.
< chemical formula 3>
Wherein R1, R2 and R3 are different from each other and are each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a dialkylamine having 1 to 6 carbon atoms, a cyclic amine group having 1 to 6 carbon atoms or a halogen atom.
The invention discloses a method for forming a thin layer, comprising the following steps: a step of supplying the aluminum precursor into a chamber in which a substrate is placed; a step of purifying the inside of the cavity; and a step of supplying a reactive substance to the inside of the chamber so that the reactive substance reacts with the aluminum precursor to form a thin layer.
The present invention discloses a method for forming a thin layer using a surface protecting substance, the method comprising: a step of supplying a metal aluminum precursor into a cavity having a substrate built therein so that the metal precursor is adsorbed onto the substrate; a step of purifying the inside of the cavity; and a step of supplying a reactive substance to the inside of the chamber to react the reactive substance with the adsorbed metal precursor to form the thin layer, wherein, before forming the thin layer, the method further comprises: a step of supplying the surface protecting substance to the inside of the cavity; and a step of purging the inside of the chamber, wherein the metal precursor is formed by mixing 1 to 3 moles of the compound represented by the following chemical formula 1 or the following chemical formula 2 and 1 to 3 moles of the compound represented by the following chemical formula 3.
< chemical formula 1>
Wherein X is O or S, R1 or R2 are each independently selected from alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms and aryl groups having 6 to 12 carbon atoms,
< chemical formula 2>
Wherein X is O or S, n is 1 to 5, R1 to R4 are each independently selected from a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms and an aryl group of 6 to 12 carbon atoms,
< chemical formula 3>
Wherein R1, R2 and R3 are different from each other and are each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a dialkylamine having 1 to 6 carbon atoms, a cyclic amine group having 1 to 6 carbon atoms or a halogen atom.
The metal precursor may be formed by combining ethyl methyl sulfide or ethyl propyl ether or tetrahydrofuran with trimethylaluminum.
The surface protecting substance may be represented by the following chemical formula 4:
< chemical formula 4>
Wherein n is each independently an integer of 0 to 6, X is O or S, R1 to R3 are each independently an alkyl group having 1 to 6 carbon atoms, and R4 is selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms.
The thin layer may be any one of alumina, aluminum nitride, aluminum sulfide.
The process may be carried out at 50 to 700 ℃.
The invention discloses a manufacturing method of a volatile memory device, which comprises the method for forming a thin layer.
The invention discloses a method for manufacturing a nonvolatile memory device, which comprises the method for forming a thin layer.
Effects of the invention
According to the present invention, a thin layer having excellent step coverage can be formed. The surface protecting species behave similarly to the metal precursor during processing and adsorb to the top (or inlet) at high density and to the bottom (or inside) at low density in high aspect ratio structures. The surface protecting substance prevents adsorption of the metal precursor in a subsequent process. Thus, the metal precursor can be uniformly adsorbed into the structure.
In particular, with excellent step coverage, even in an ultra-high stacked structure, a high purity thin film free of impurities can be formed while reducing the difference in the uppermost and lowermost characteristics of the unit cell, and the electrical characteristics and reliability of the device can be improved.
In addition, the aluminum precursor can be prevented from spontaneous combustion due to exposure to air, and stable gas phase delivery to the substrate surface can be achieved due to excellent thermal stability.
In particular, the effect thereof is maximized by introducing it together with the surface protecting substance, thereby minimizing the deposition thickness per cycle for easy control of the thickness, and the deposited film can ensure excellent uniformity and step coverage.
Drawings
FIG. 1 is a 1H-NMR chart of precursor X1 according to example 1 of the invention.
FIG. 2 is an H-NMR chart of precursor X2 according to example 2 of the invention.
FIG. 3 is an H-NMR chart of precursor Y2 according to example 3 of the invention.
Fig. 4 to 9 are graphs showing the Differential Scanning Calorimetry (DSC) test results and thermogravimetric analysis (TGA) test results of examples 1 to 3.
Fig. 10 is a photograph showing the results of the outdoor air exposure test of examples 1 to 3.
Fig. 11 is a graph showing weight changes after exposure to outdoor air in examples 2 to 3.
Fig. 12 is a schematic diagram comparing TMA with an embodiment of the present invention.
Fig. 13 is a graph showing GPC (per cycle growth) of the aluminum oxide films according to comparative examples 1 and 2 of the present invention with process temperature.
Fig. 14 is a flowchart schematically illustrating a method of forming a thin layer according to an embodiment of the present invention.
Fig. 15 is a graph schematically showing a supply cycle according to an embodiment of the present invention.
Fig. 16 is a graph showing weight change after exposure to outdoor air in examples 2 and 4.
Fig. 17 is a graph showing the result of mixing the precursor TMA and the surface protecting substance TMOF into a liquid phase corresponding to comparative example 1-1.
FIG. 18 is a graph showing the result of mixing the precursor TMA-THF and the surface protecting substance TMOF into a liquid phase corresponding to comparative example 4-1.
Fig. 19 and 20 are GPC (amount of growth per cycle) showing the increase in the alumina film with the precursor supply time at the same deposition temperature.
Fig. 21 is a graph showing XPS depth distribution for analyzing the surface of an aluminum oxide film according to an embodiment of the present invention.
Fig. 22 is a result of depositing an aluminum oxide film on a pattern wafer to confirm step coverage according to an embodiment of the present invention.
Detailed Description
Next, an embodiment of the present invention will be described with reference to fig. 1 to 22. The described embodiments of the invention may include various modifications and the scope of the invention should not be construed as being limited to the embodiments described below.
According to the present invention, a method of forming a thin layer includes; a step of supplying an aluminum precursor into a chamber in which a substrate is placed; a step of purifying the inside of the cavity; and supplying a reactive substance into the chamber so that the reactive substance reacts with the aluminum precursor to form a thin layer.
At this time, the supply of the aluminum precursor and the formation of the thin layer are performed at 50 to 700 ℃. Further, the thin layer may be any one of aluminum oxide, aluminum nitride, and aluminum sulfide.
According to the present invention, the aluminum precursor is formed by mixing 1 to 3 moles of the compound represented by the following chemical formula 1 or the following chemical formula 2 and 1 to 3 moles of the compound represented by the following chemical formula 3.
< chemical formula 1>
Wherein X is O or S, and R1 or R2 are each independently selected from alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 12 carbon atoms.
< chemical formula 2>
Wherein X is O or S, n is 1 to 5, and R1 to R4 are each independently selected from a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.
< chemical formula 3>
Wherein R1, R2 and R3 are different from each other and are each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a dialkylamine having 1 to 6 carbon atoms, a cyclic amine group having 1 to 6 carbon atoms or a (cyclic amine group) halogen atom.
The aluminum precursor may be formed by mixing ethyl methyl sulfide and trimethylaluminum.
The aluminum precursor may be formed by mixing ethyl propyl ether and trimethylaluminum.
Example 1
In a storage box at room temperature, 5.28g (0.069 mol) of ethyl methyl sulfide was added to a 500ml round flask, and 5g (0.069 mol) of trimethylaluminum was added very slowly to obtain precursor X1.
FIG. 1 is a 1H-NMR chart of precursor X1 according to example 1 of the invention, and shows the nuclear magnetic resonance spectrum of example 1/ethylmethyl sulfide/trimethylaluminum.
Peaks of chemical shifts δ=2.19 ppm, 1.76ppm, and 1.20ppm by ethyl methyl sulfide were shifted to 1.92ppm, 1.41ppm, and 0.69ppm, respectively, without changing the peak morphology even after formation of the precursor X1.
It was found that, after the precursor X1 was formed, the peak of the chemical shift δ= -0.36ppm by trimethylaluminum was finely moved without changing the morphology thereof to form a stable precursor. Ha (9H): the integral rate of Hb (3H) is about 9:2.8, it was confirmed that one molecule of ethylmethyl sulfide forms a precursor.
Example 2: preparation of TMA-EMS
In a storage box at room temperature, 10.56g (0.139 mol) of ethyl methyl sulfide was added to a 500ml round flask, and 5g (0.069 mol) of trimethylaluminum was added very slowly to obtain precursor X2 (TMA-EMS).
FIG. 2 is a H-NMR chart of precursor X2 of example 2 according to the invention, showing the nuclear magnetic resonance spectrum of example 2/ethylmethyl sulfide/trimethylaluminum.
Peaks of chemical shifts δ=2.19 ppm, 1.76ppm, and 1.20ppm by ethyl methyl sulfide were shifted to 2.05ppm, 1.58ppm, and 0.85ppm, respectively, without changing the peak morphology even after formation of the precursor X2.
It was confirmed that δ=2.19 ppm, 1.76ppm, and 1.20ppm chemical shift peaks generated by EMS were transferred to 2.05ppm, 1.58ppm, and 0.85ppm, respectively, even without changing peak morphology after precursor formation.
It is understood that, after the formation of the precursor X2, the peak of the chemical shift δ= -0.36 by trimethylaluminum also moves finely without changing the morphology thereof, thereby forming a stable precursor. Confirmation Ha (9H): the integral rate of Hb (3H) is about 9:5.7,2 molecules of ethyl methyl sulfide form the precursor.
Example 3
In a storage box at room temperature, 12.23g (0.139 mol) of ethyl propyl ether was added to a 500ml round flask, and 5g (0.069 mol) of trimethylaluminum was added very slowly to obtain precursor Y2.
FIG. 3 is an H-NMR chart of precursor Y2 of example 3 according to the invention, showing the nuclear magnetic resonance spectrum of example 3/ethyl propyl ether/trimethylaluminum.
Peaks of chemical shifts δ=0.89 ppm, 1.12ppm, and 1.55ppm due to ethyl propyl ether were shifted to 0.89ppm, and 1.35ppm, respectively, without changing the peak morphology even after formation of the precursor Y2.
It was found that, after the formation of the precursor Y2, the peak of the chemical shift δ= -0.36ppm by trimethylaluminum was finely moved without changing the morphology, and a stable precursor was formed. Confirmation Ha (9H): the integral rate of Hb (3H) is about 9:5.7,2 molecules of ethyl propyl ether form the precursor.
Thermal analysis
Fig. 4 to 9 are graphs showing the Differential Scanning Calorimetry (DSC) test results and thermogravimetric analysis (TGA) test results of examples 1 to 3. Differential Scanning Calorimetry (DSC) test and thermogravimetric analysis (TGA) test were performed on X1, X2, Y2 obtained in examples 1 to 3, and the thermal analysis test conditions for measuring the thermal decomposition temperature in each test were as follows.
Conveying gas: argon (Ar)
Delivery gas flow rate: 200ml/min
Heating profile: heating from 30 ℃ to 500 ℃ at a heating rate of 10 ℃/min.
In the DSC test, the thermal decomposition temperature is determined as the temperature at the point in the DSC thermogram where the heat flow suddenly increases as the temperature increases.
Referring to the following [ Table 1], X1 and X2 each have excellent vaporization characteristics, and the residual component amount is 0.1% or less, leaving no impurities in the thin layer. In addition, the decomposition temperature is higher than 340 ℃, and the organic molecules effectively block al—al interactions between TMAs, resulting in a high decomposition temperature and improved thermal stability, compared to the case where only TMA is used, and thus, can be transferred to the surface of the substrate in a stable gas phase.
TABLE 1
| T1/2(℃) | TGA residue (%) | DSC decomposition temperature (. Degree. C.) | |
| TMA | 66 | <0.1 | 319 |
| X1 | 103 | <0.1 | 346 |
| X2 | 99 | <0.1 | 343 |
| Y2 | 113 | 1.1 | 344 |
Furthermore, although X2 has a larger molecular weight than X1, the vaporization characteristic is further improved, and thus, it seems that two molecules of an organic substance effectively block al—al interaction between TMAs, X2 is more suitable in terms of stability.
In addition, Y2 was also confirmed to have vaporization characteristics suitable for use as an ALD precursor due to the two molecular blocking effect, and its decomposition temperature was higher than 344 ℃ with improved thermal stability compared to TMA alone, and thus, can be delivered to the surface of the substrate in a stable gas phase.
Outdoor exposure test
Fig. 10 is a photograph showing the results of the outdoor air exposure test of examples 1 to 3. Equal amounts of X1, X2 and Y2 obtained in examples 1-3 were exposed to room temperature/pressure. In the case of X1, the combustion is immediate in the state of being exposed to the inside of the straw, but in the case of X2/Y2, only fine smoke is generated and not burned. It was confirmed that the air-in-air combustibility was greatly reduced and that the air-in-air combustion did not occur. The suppression of spontaneous combustion of X2/Y2 compared with X1 can be considered as an effect of forming a very stable substance by completely blocking an empty P-orbital (empty P-orbital) of Al with two molecules.
Fig. 11 is a graph showing weight changes after exposure to outdoor air in examples 2 to 3. As a result of the same amount of X2/Y2 exposed to the outdoor air, in the case of Y2, its weight was rapidly reduced and all cured after 5 hours, and no further weight change occurred. However, in the case of X2, the weight reduction rate was relatively slow, and after 7 hours, it was all cured, and no more weight change occurred.
In both cases, oxidation reactions occur, but no ignition occurs, so stability at disposal increases substantially and the risk of failure can be reduced rapidly.
The outdoor exposure test in fig. 10 and 11 can be considered similar to the chemical reaction of adsorbing the precursor at the surface. When exposed to the outside air, the precursor reacts with H2O in the air and undergoes a chemical reaction that breaks al—c bonds and replaces al—o bonds. This is because the reaction where it meets the-OH terminated surface of the oxide film and the precursor and the ligand drops off and is adsorbed is very similar.
As is apparent from the results of fig. 10 and 11, the empty P orbitals of Al are completely blocked by the organic matters in all the X2 and Y2 precursors of the above-described examples, and thus, the oxidation reaction occurs very slowly and the reactivity is greatly reduced even when exposed to the outdoor air. The slow reactivity of the fully blocked precursor can be confirmed by the schematic diagram of fig. 12.
In addition, the diameter of the X2 precursor is aboutThis is +.>Compared to that, the size is greatly increased. This not only further reduces the tableThe accessibility of the surface-OH to the Al center of the X2 precursor also reduces the deposition thickness per cycle due to the greater steric hindrance when some of the adsorbed precursor is present on the surface. This can be confirmed by the deposition results using the X2 precursor in fig. 13.
Also, the-OH end groups and reactivity of the X2 and Y2 precursor surfaces are reduced, resulting in reduced adhesion coefficient and increased surface diffusion, thereby forming a uniform film, and eventually, improved uniformity and step coverage.
Comparative example 1: TMA deposition results
An aluminum oxide film is formed on a silicon substrate. The aluminum oxide film is formed by an ALD process at a temperature of 250-400 c with O3 gas as a reactive species.
The process of forming an aluminum oxide film by the ALD process is as follows, and the following process is performed as one cycle.
1) Ar is used as a carrier gas, and an aluminum precursor TMA (trimethylaluminum) is supplied to the reaction chamber at room temperature, the aluminum precursor being adsorbed onto the substrate.
2) Argon is supplied to the reaction chamber to purge the unadsorbed aluminum precursor or byproduct.
3) O3 gas is supplied to the reaction chamber to form a monolayer.
4) Argon is supplied to the reaction chamber to discharge unreacted materials or byproducts.
As a result of measuring the thickness of the aluminum oxide film obtained by the above-mentioned process, the thickness of the aluminum oxide film obtained for each cycle of the ALD process is about 250 to 400 DEG CCycle.
Fig. 13 is a graph showing GPC (amount of growth per cycle) with process temperature of the aluminum oxide films of comparative examples 1 and 2 according to the present invention. As shown in fig. 13, the desirable ALD behavior of GPC with small variations with rising substrate temperature was exhibited in the substrate temperature range of 250 to 400 ℃. Suppose ZrO of DRAM 2 /Al 2 O 3 /ZrO 2 The total thickness of the dielectric film in the composite dielectric film isAnd Al2O3 of comparative example 1 was used for about 3 cycles, the dielectric film had an EOT of +.>
Example 2: deposition results of TMA-EMS
An aluminum oxide film was formed on a silicon substrate using the precursor X2 according to example 2 of the present invention. An aluminum oxide film was formed in the same manner as in comparative example 1, except that the precursor was replaced.
The thickness of the aluminum oxide film obtained by the above procedure was measured to be about that obtained for each cycle of the ALD process at 250 to 400 cAnd (3) a period.
Further, as shown in fig. 13, in the substrate temperature range of 250 to 400 ℃, the desirable ALD behavior of GPC with small variation with the rise of the substrate temperature was exhibited, and the effect of reduction by about 20% compared to comparative example 1 was exhibited.
Suppose ZrO of DRAM 2 /Al 2 O 3 /ZrO 2 The total thickness of the dielectric film in the composite dielectric film isAnd Al2O3 of example 2 was used for about 3 cycles, then the dielectric film had an EOT of +.>Ensuring a scaling down of about 4% compared to comparative example 1.
On the other hand, in the conventional deposition process using a single precursor, in a trench structure having a high aspect ratio (e.g., 40:1 or more), a thin layer deposited on an upper portion (or an inlet) of the trench becomes thicker, and a thin layer deposited on a lower portion (or a bottom) of the trench becomes thinner. Therefore, the step coverage of the thin layer is poor and uneven.
However, the surface protecting substance described below has the same behavior as the metal precursor, and is adsorbed at a higher density in the upper portion of the trench than in the lower portion of the trench, thereby impeding the adsorption of the metal precursor in the subsequent process, and thus the metal precursor reacts with the reactive substance to form the thin layer having a uniform thickness in the trench.
Fig. 14 is a flowchart schematically illustrating a method of forming a thin layer according to an embodiment of the present invention, and fig. 15 is a graph schematically illustrating a supply cycle according to an embodiment of the present invention. The substrate is loaded into the process chamber and the following ALD process conditions are adjusted. ALD process conditions may include the temperature of the substrate or process chamber, the pressure within the process chamber, and the gas flow rate, with temperatures in the range of 50-700 ℃.
The substrate is exposed to the surface protecting substance supplied to the inside of the cavity, and the surface protecting substance is adsorbed onto the surface of the substrate. During deposition, the surface protecting species has a similar behavior as the metal precursor, and the trench structure has a high aspect ratio (e.g., 40:1 or more), adsorbing at the entrance of the trench with a high density and adsorbing at the bottom of the trench with a low density, thereby impeding the adsorption of the metal precursor in subsequent processes.
Specifically, the metal precursor is formed by mixing 1 to 3 moles of the compound represented by the following chemical formula 1 or the following chemical formula 2 and 1 to 3 moles of the compound represented by the following chemical formula 3.
< chemical formula 1>
Wherein X is O or S, and R1 or R2 are each independently selected from alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 12 carbon atoms.
< chemical formula 2>
Wherein X is O or S, n is 1 to 5, and R1 to R4 are each independently selected from a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms.
< chemical formula 3>
Wherein R1, R2 and R3 are different from each other and are each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a dialkylamine having 1 to 6 carbon atoms, a cyclic amine group having 1 to 6 carbon atoms or a halogen atom.
The metal precursor may be formed by mixing ethyl methyl sulfide or ethyl propyl ether or tetrahydrofuran with trimethylaluminum.
Furthermore, the surface protecting substance may be represented by the following chemical formula 4.
< chemical formula 4>
Wherein n is each independently an integer of 0 to 6, X is O or S, R1 to R3 are each independently an alkyl group having 1 to 6 carbon atoms, and R4 is selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms.
Thereafter, a purge gas (e.g., an inert gas such as Ar) is supplied into the chamber interior to discharge the non-adsorbed surface protecting substance or by-product.
Thereafter, the substrate is exposed to a metal precursor supplied to the inside of the cavity, the metal precursor being adsorbed onto the surface of the substrate. The metal precursor is supplied at 50-700 ℃.
For example, the surface protecting substance described above is adsorbed at the entrance of the trench to be denser than at the bottom of the trench, and the metal precursor cannot be adsorbed to the position where the surface protecting substance is adsorbed. That is, in the conventional deposition process, the metal precursor is more densely adsorbed at the entrance of the trench than at the bottom of the trench, thereby having a high density at the entrance of the trench. However, in the present invention, the surface protecting substance is adsorbed more densely at the entrance of the trench than at the bottom of the trench, thereby hindering the adsorption of the metal precursor at the entrance of the trench, and therefore, the metal precursor can be uniformly adsorbed into the trench without excessive adsorption at the entrance of the trench, and the step coverage of a thin layer to be described later is improved.
Thereafter, a purge gas (e.g., an inert gas such as Ar) is supplied into the chamber interior to exhaust the metal precursor or by-product that is not adsorbed.
Thereafter, the substrate is exposed to a reactive substance supplied to the inside of the cavity, and a thin layer is formed on the surface of the substrate. The reactant reacts with the metal precursor to form the thin layer, and the reactant may be water vapor (H2O), oxygen (O2), and ozone (O3). The metal oxide film may be formed by a reaction. At this time, the reactive species oxidize the adsorbed surface-protecting species, and the adsorbed surface-protecting species may be separated and removed from the surface of the substrate. The thin layer is formed at 50-700 deg.c, and may be any one of alumina, aluminum nitride and aluminum sulfide.
Thereafter, a purge gas (e.g., an inert gas such as Ar) is supplied into the chamber interior to expel the surface protecting substance/unreacted material or byproducts.
On the other hand, it has been explained above that the surface protecting substance is supplied before the metal precursor. Alternatively, the surface protecting substance may be supplied after the metal precursor, or the metal precursor may be supplied both before and after the surface protecting substance.
Comparative example 1-1: deposition results Using TMA and surface protecting substance TMOF
On a silicon substrate, an aluminum oxide film was formed using trimethyl orthoformate (TMOF) as a surface protecting substance based on the above < chemical formula 4 >. The aluminum oxide film was formed in the same manner as in comparative example 1, except that the surface protective substance was used.
The process of forming the alumina layer by the ALD process is as follows, and the following process is performed as one cycle.
1) The surface protecting substance is supplied to the reaction chamber to be adsorbed onto the substrate.
2) Argon is supplied to the reaction chamber to purge non-adsorbed surface protecting substances or byproducts.
3) Ar is used as a carrier gas, the aluminum precursor is supplied to the reaction chamber at room temperature, and the aluminum precursor is adsorbed onto the substrate.
4) Argon is supplied to the reaction chamber to purge the non-adsorbed aluminum precursor or by-product.
5) O3 gas is supplied to the reaction chamber to form a monolayer.
6) Argon is supplied to the reaction chamber to discharge unreacted materials or byproducts.
Example 2-1: deposition results Using TMA-EMS and surface protecting substance TMOF
On the silicon substrate, an aluminum oxide film was formed using trimethyl orthoformate (TMOF) as a surface protecting substance based on the above < chemical formula 4 >. An aluminum oxide film was formed in the same manner as in comparative example 1-1, except that the precursor was replaced.
Example 4: TMA-THF manufacture and deposition results
Based on < chemical formula 2> of the present invention, an Al precursor is formed by mixing THF (tetrahydrofuran) and TMA. In a storage box at room temperature, 10g (0.139 mol) of tetrahydrofuran was added to a 500ml round flask, and 10g (0.139 mol) of trimethylaluminum was very slowly added to obtain a precursor TMA-THF.
It was confirmed that δ=3.57 ppm and 1.42ppm chemical shift peaks generated by EMS were transferred to 3.35ppm and 0.96ppm, respectively, even in the case that the shape of the peaks was unchanged after the precursor was formed, thereby forming a stable material.
An aluminum oxide film was formed on a silicon substrate using the TMA-THF produced. An aluminum oxide film was formed in the same manner as in comparative example 1, except that the precursor was replaced.
Example 4-1: deposition results Using TMA-THF and surface protecting substance TMOF
Based on the above < chemical formula 4>, an aluminum oxide film was formed on a silicon substrate using trimethyl orthoformate (TMOF), respectively, as a surface protecting substance. An aluminum oxide film was formed in the same manner as in comparative example 1-1, except that the precursor was replaced.
Outdoor exposure test
Fig. 16 is a graph showing weight change after exposure to outdoor air in examples 2 and 4. It was confirmed that the combustibility of the precursor in air was rapidly reduced, and that the precursor was not ignited even in air and existed in a liquid state. The suppression of spontaneous combustion can be regarded as the following effect: by completely blocking the empty P-orbitals with organic molecules, very stable species are formed.
It is known that the weight loss of the precursor is very slow and the oxidation reaction rate is slow. The outdoor exposure test can be considered similar to the chemical reaction in which the precursor is adsorbed to the surface. When exposed to the outside air, the precursor reacts with H2O in the air and is broken through Al-C bonds and replaced by chemical reactions of Al-O bonds. This is because it is very similar to the reaction that the surface of the oxide film terminating-OH and the precursor are mixed and their ligands fall off and are adsorbed. Therefore, it is inferred that the phenomenon of decreasing the reactivity of the Al precursor in air also occurs in the surface reaction.
Fig. 17 is a graph showing the result of mixing the precursor TMA and the surface protecting substance TMOF into a liquid phase corresponding to comparative example 1-1. In order to simulate the reaction of the surface protecting substance on the surface, the precursor and the surface protecting substance corresponding to comparative example 1-1 were mixed into a liquid phase.
After slowly adding 1 equivalent of trimethylaluminum to 6 equivalents of trimethyl orthoformate, the mixture was stirred thoroughly. Peak distribution was performed by 1H NMR (C6D 6) analysis of the mixture.
TMOF，HC(OCH 3 ) 2 ：δ4.82(s)，3.12(s)
(CH 3 ) 2 Al(OCH 3 )：δ3.05(s)，-0.57(s)
CH 3 CH(OCH 3 ) 2 ：δ4.42(m)，3.10(s)，1.17(d)
Due to the excessive addition of trimethyl orthoformate, δ4.82 and 3.12 generated from unreacted surface protecting substances were confirmed, confirming the product peaks formed by the ligand substitution reaction between the precursor and the surface protecting substances. It was confirmed that delta-0.36 produced by trimethylaluminum before the reaction disappeared and the reaction was ended.
FIG. 18 is a graph showing the result of mixing the precursor TMA-THF and the surface protecting substance TMOF into a liquid phase corresponding to comparative example 4-1. The precursor and the surface protecting substance corresponding to embodiment 4-1 are mixed into a liquid phase.
After 1 equivalent of TMA-THF was slowly added to 1 equivalent of trimethyl orthoformate, the mixture was stirred thoroughly. Peak distribution was performed by 1H NMR (C6D 6 analysis) of the mixture.
TMOF，HC(OCH 3 ) 2 ：δ4.82(s)，3.12(s)
TMA-THF：δ3.43(m)，δ1.16(m)，-0.39(s)
(CH 3 ) 2 Al(OCH 3 )：δ3.05(s)，-0.57(s)
CH 3 CH(OCH 3 ) 2 ：δ4.42(m)，3.10(s)，1.17(d)
The product peaks formed by the ligand substitution reaction of the precursor and the surface protecting substance were confirmed to be in the same form as the previous results. However, it was confirmed that TMA-THF/trimethyl orthoformate peaks did not react unlike the case where all trimethylaluminum precursor reacted and disappeared. This can be explained by the very slow reactivity of TMA-THF and the surface protecting species, and it leads to a reduced adhesion coefficient during deposition, an increased diffusion of the surface in the surface reaction, and an improved step coverage compared to conventional precursors.
Table 2 shows GPC (amount of growth per cycle) of the aluminum oxide films according to comparative examples and examples 2 and 4 of the present invention.
TABLE 2
Comparing the GPC of the Al precursor without the surface protecting material, it is found that the GPC of examples 2 and 4 were reduced by 26% and 23%, respectively, compared with the case of using TMA alone. This can be explained as: the reactivity of the precursor is reduced due to the Al blocking effect; and the accessibility of Al centers and surface-OH is reduced due to the increased size compared to MA.
The reduced reactivity with-OH end groups on the surface results in reduced adhesion coefficient and increased diffusion on the surface to form a uniform film, with improved final uniformity and step coverage.
It is known that GPC reduction of Al precursor using the surface protecting substance is further maximized. In comparative example 1-1, when the reduction rate was 30% when only the surface protecting substance was applied, and in example 4-1, when both the TMA-THF precursor of the present invention and the surface protecting substance were applied, it was confirmed that the reduction rate was greatly increased to a high reduction rate of 70%.
Suppose ZrO of DRAM 2 /Al 2 O 3 /ZrO 2 The total thickness of the dielectric film in the composite dielectric film isAnd Al2O3 of example 2-1 was used for about 3 cycles, the dielectric film had an EOT of +.>A proportional reduction of about 12% can be achieved compared to the case where only TMA is used in comparative example 1.
Fig. 19 and 20 show GPC (amount of growth per cycle) of aluminum oxide films at the same deposition temperature with increasing precursor feed time.
In the comparative example of fig. 19, as the precursor supply time increases, GPC to which the surface protecting substance is applied continues to increase, and therefore, the saturation characteristic is not good and is not easy to control. On the other hand, the GPC using the surface protecting substance in the embodiment of fig. 20 has very slow GPC compared with the process using only the precursor, and exhibits a saturation characteristic in which GPC changes little even when the precursor supply time is increased, which is suitable for the ALD process.
Fig. 21 is a graph showing XPS depth distribution for analyzing the surface of an aluminum oxide film according to an embodiment of the present invention. The carbon content in the thin layer was 0%, forming a thin layer free of impurities.
Fig. 22 is a result of depositing an aluminum oxide film on a pattern wafer to confirm step coverage (aspect ratio 20:1) according to an embodiment of the present invention. In all the examples, it was confirmed that the excellent characteristics were exhibited at a step coverage of 100%.
In summary, by applying the above Al precursor and the surface protecting substance of the present invention, a high GPC reduction effect can be obtained, and accordingly, precise thickness control and excellent step coverage can be obtained, while the electrical characteristics and reliability of the device can be improved. In addition, a thin layer of high purity free of impurities can be formed, and the thin layer is thinner than one monolayer that can be obtained by the existing ALD process.
The invention has been described in detail with reference to embodiments, but may also include other embodiments. Accordingly, the technical idea and scope described in the following claims are not limited to the above-described embodiments.
Claims (16)
1. A method for producing an aluminum precursor, wherein 1 to 3 moles of a compound represented by the following chemical formula 1 or the following chemical formula 2 and 1 to 3 moles of a compound represented by the following chemical formula 3 are mixed to form the aluminum precursor,
< chemical formula 1>
Wherein x is O or S, R1 or R2 are each independently selected from alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 12 carbon atoms,
< chemical formula 2>
Wherein X is O or S, n is 1 to 5, R1 to R4 are each independently selected from a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms and an aryl group of 6 to 12 carbon atoms,
< chemical formula 3>
Wherein R1, R2 and R3 are different from each other and are each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a dialkylamine having 1 to 6 carbon atoms, a cyclic amine group having 1 to 6 carbon atoms or a halogen atom.
2. The method of manufacturing an aluminum precursor according to claim 1, wherein ethyl methyl sulfide and trimethylaluminum are mixed to form the aluminum precursor.
3. The method of manufacturing an aluminum precursor as recited in claim 1, wherein ethyl propyl ether and trimethylaluminum are mixed to form the aluminum precursor.
4. An aluminum precursor is formed by mixing 1 to 3 moles of a compound represented by the following chemical formula 1 or the following chemical formula 2 and 1 to 3 moles of a compound represented by the following chemical formula 3,
< chemical formula 1>
Wherein X is O or S, R1 or R2 are each independently selected from alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms and aryl groups having 6 to 12 carbon atoms,
< chemical formula 2>
Wherein X is O or S, n is 1 to 5, R1 to R4 are each independently selected from a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms and an aryl group of 6 to 12 carbon atoms,
< chemical formula 3>
Wherein R1, R2 and R3 are different from each other and are each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a dialkylamine having 1 to 6 carbon atoms, a cyclic amine group having 1 to 6 carbon atoms or a halogen atom.
5. A method of forming a thin layer, comprising:
a step of supplying the aluminum precursor of claim 4 into a chamber in which a substrate is placed;
a step of purifying the inside of the cavity; and
And a step of supplying a reactive substance to the inside of the chamber so that the reactive substance reacts with the aluminum precursor to form a thin layer.
6. The method of forming a thin layer as claimed in claim 5, wherein the thin layer is one of aluminum oxide, aluminum nitride and aluminum sulfide.
7. The method for forming a thin layer as claimed in claim 5, wherein the method is performed at 50 to 700 ℃.
8. A method of manufacturing a volatile memory device, comprising the method of forming a thin layer according to claim 5.
9. A method of manufacturing a nonvolatile memory device, comprising the method of forming a thin layer according to claim 5.
10. A method of forming a thin layer using a surface protecting substance, comprising:
a step of supplying a metal aluminum precursor into a cavity having a substrate built therein so that the metal precursor is adsorbed onto the substrate;
a step of purifying the inside of the cavity; and
A step of supplying a reactive substance to the inside of the chamber so that the reactive substance reacts with the adsorbed metal precursor to form the thin layer,
wherein, prior to forming the thin layer, the method further comprises:
a step of supplying the surface protecting substance to the inside of the cavity; and
A step of purifying the inside of the cavity,
wherein the metal precursor is formed by mixing 1 to 3 moles of a compound represented by the following chemical formula 1 or the following chemical formula 2 and 1 to 3 moles of a compound represented by the following chemical formula 3,
< chemical formula 1>
Wherein X is O or S, R1 or R2 are each independently selected from alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms and aryl groups having 6 to 12 carbon atoms,
< chemical formula 2>
Wherein X is 0 or S, n is 1 to 5, R1 to R4 are each independently selected from a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms and an aryl group of 6 to 12 carbon atoms,
< chemical formula 3>
Wherein R1, R2 and R3 are different from each other and are each independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a dialkylamine having 1 to 6 carbon atoms, a cyclic amine group having 1 to 6 carbon atoms or a halogen atom.
11. The method of forming a thin layer using a surface protecting substance according to claim 10, wherein ethyl methyl sulfide, ethyl propyl ether or tetrahydrofuran is mixed with trimethylaluminum to form the metal precursor.
12. The method for forming a thin layer using a surface protective substance according to claim 10, wherein the surface protective substance is represented by the following chemical formula 4:
< chemical formula 4>
Wherein n is each independently an integer of 0 to 6, X is O or S, R1 to R3 are each independently an alkyl group having 1 to 6 carbon atoms, and R4 is selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkylthio group having 1 to 6 carbon atoms.
13. The method of forming a thin layer using a surface protecting substance according to claim 10, wherein the thin layer is one of aluminum oxide, aluminum nitride and aluminum sulfide.
14. A method of forming a thin layer using a surface protecting substance as claimed in claim 10, wherein the method is carried out at 50 to 700 ℃.
15. A method of manufacturing a volatile memory device, comprising a method of forming a thin layer based on any one of claims 10 to 14.
16. A method of manufacturing a non-volatile memory device, comprising a method of forming a thin layer based on any of claims 10 to 14.
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