KR101772478B1 - Organic group 13 precursor and method for depositing thin film using thereof - Google Patents
Organic group 13 precursor and method for depositing thin film using thereof Download PDFInfo
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- KR101772478B1 KR101772478B1 KR1020150132938A KR20150132938A KR101772478B1 KR 101772478 B1 KR101772478 B1 KR 101772478B1 KR 1020150132938 A KR1020150132938 A KR 1020150132938A KR 20150132938 A KR20150132938 A KR 20150132938A KR 101772478 B1 KR101772478 B1 KR 101772478B1
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- 239000002243 precursor Substances 0.000 title claims abstract description 92
- 125000000962 organic group Chemical group 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims description 48
- 238000000151 deposition Methods 0.000 title claims description 27
- 239000010409 thin film Substances 0.000 title claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 45
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 27
- 229910052795 boron group element Inorganic materials 0.000 claims abstract description 19
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000010408 film Substances 0.000 claims description 116
- 229910052782 aluminium Inorganic materials 0.000 claims description 71
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 65
- 239000000758 substrate Substances 0.000 claims description 54
- 238000005137 deposition process Methods 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 20
- 229910052733 gallium Inorganic materials 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000005229 chemical vapour deposition Methods 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000007736 thin film deposition technique Methods 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000012495 reaction gas Substances 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910002601 GaN Inorganic materials 0.000 claims description 7
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 7
- 239000012159 carrier gas Substances 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 5
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 35
- -1 pyrrolidino diethyl gallium Chemical compound 0.000 description 29
- 238000000113 differential scanning calorimetry Methods 0.000 description 27
- 238000005160 1H NMR spectroscopy Methods 0.000 description 24
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 21
- 238000002076 thermal analysis method Methods 0.000 description 19
- 238000004458 analytical method Methods 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 230000008021 deposition Effects 0.000 description 15
- 125000001424 substituent group Chemical group 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 12
- 238000000427 thin-film deposition Methods 0.000 description 11
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 10
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 9
- SSAWPNVUGVLDQP-UHFFFAOYSA-N n-diethylalumanyl-n-ethylethanamine Chemical compound CC[N-]CC.CC[Al+]CC SSAWPNVUGVLDQP-UHFFFAOYSA-N 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
- OIVNKLGZDUDINX-UHFFFAOYSA-N diethyl(pyrrolidin-1-yl)alumane Chemical compound CC[Al](CC)N1CCCC1 OIVNKLGZDUDINX-UHFFFAOYSA-N 0.000 description 8
- 238000010926 purge Methods 0.000 description 8
- 238000000197 pyrolysis Methods 0.000 description 8
- 238000000231 atomic layer deposition Methods 0.000 description 7
- GTLMIIKASNFJDX-UHFFFAOYSA-N diethylalumanylium;dimethylazanide Chemical compound C[N-]C.CC[Al+]CC GTLMIIKASNFJDX-UHFFFAOYSA-N 0.000 description 7
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 7
- QAIDPMSYQQBQTK-UHFFFAOYSA-N diethylgallium Chemical compound CC[Ga]CC QAIDPMSYQQBQTK-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 4
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 4
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 4
- BKIVQXZTWLSKAY-UHFFFAOYSA-N 1-[amino(ethyl)alumanyl]-2-methylbutane Chemical compound C(C)C(C[Al](CC)N)C BKIVQXZTWLSKAY-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- SNCWMPNFDOCCJW-UHFFFAOYSA-N C(C)CC[Al](CC)NC Chemical compound C(C)CC[Al](CC)NC SNCWMPNFDOCCJW-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000002259 gallium compounds Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- JCFWQQBAXPSTGF-UHFFFAOYSA-N 1-[amino(ethyl)alumanyl]-2-methylpropane Chemical compound CC(C[Al](CC)N)C JCFWQQBAXPSTGF-UHFFFAOYSA-N 0.000 description 1
- LLWATWLAZDZEMY-UHFFFAOYSA-N N-dihexadecylalumanyl-N-methylmethanamine Chemical compound CN(C)[Al](CCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCC LLWATWLAZDZEMY-UHFFFAOYSA-N 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- VYBYZVVRYQDCGQ-UHFFFAOYSA-N alumane;hafnium Chemical compound [AlH3].[Hf] VYBYZVVRYQDCGQ-UHFFFAOYSA-N 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 description 1
- MIQVEZFSDIJTMW-UHFFFAOYSA-N aluminum hafnium(4+) oxygen(2-) Chemical compound [O-2].[Al+3].[Hf+4] MIQVEZFSDIJTMW-UHFFFAOYSA-N 0.000 description 1
- VQYHBXLHGKQYOY-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[Al+3].[Ti+4] VQYHBXLHGKQYOY-UHFFFAOYSA-N 0.000 description 1
- HVXCTUSYKCFNMG-UHFFFAOYSA-N aluminum oxygen(2-) zirconium(4+) Chemical compound [O-2].[Zr+4].[Al+3] HVXCTUSYKCFNMG-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000007416 differential thermogravimetric analysis Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
-
- H01L21/205—
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The organic Group 13 precursor according to one embodiment of the present invention is represented by the following Chemical Formula 1.
≪ Formula 1 >
Wherein M is any one selected from the metal elements belonging to Group 13 elements in the periodic table, L 1 and L 2 are each independently selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms And R 1 and R 2 are each independently any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms.
Description
More particularly, the present invention relates to an aluminum precursor capable of effectively forming an aluminum-containing film, a method of depositing an aluminum-containing film using the precursor, a gallium precursor capable of effectively forming a gallium- And a method of depositing gallium-containing films using the same.
BACKGROUND ART In order to manufacture miniaturized electronic devices to meet miniaturization, low power, and high capacity of electronic devices due to development of electronic technology, miniaturization of various electronic devices including metal oxide semiconductor (MOC) devices is required.
Precursors containing Group 13 elements are precursors with excellent stability and conductivity, and are receiving the spotlight as precursors for thin film deposition. In particular, precursors containing Group 13 elements are being actively utilized in metal organic chemical vapor deposition (MOCVD) and atomic layer deposition (ALD) processes. In order to ensure the properties of the thin film deposited in the MOCVD or ALD process, the precursor comprising the Group 13 element to be supplied must be thermally stable and have a high vapor pressure at low temperatures.
An object of the present invention is to provide an aluminum precursor capable of effectively forming an aluminum-containing film and a method of depositing an aluminum-containing film using the same.
Another object of the present invention is to provide a gallium precursor capable of effectively forming a gallium-containing film and a method of depositing a gallium-containing film using the same.
Other objects of the present invention will become more apparent from the following detailed description.
The organic Group 13 precursor according to one embodiment of the present invention is represented by the following Chemical Formula 1.
≪ Formula 1 >
Wherein M is any one selected from the metal elements belonging to Group 13 elements in the periodic table, L 1 and L 2 are each independently selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms And R 1 and R 2 are each independently any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms.
The organic Group 13 precursor may be represented by Formula 2 below.
(2)
Wherein L 1 and L 2 are each independently any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms and R 1 and R 2 each independently represent an alkyl group having 1 to 6 carbon atoms , And a cycloalkyl group having 3 to 6 carbon atoms.
The organic Group 13 precursor may be represented by Formula 3 below.
(3)
The organic Group 13 precursor may be represented by Formula 4 below.
≪ Formula 4 >
The organic group 13 precursor may be represented by the following formula (5).
≪ Formula 5 >
The organic Group 13 precursor may be represented by Formula 6 below.
(6)
In the above formula (6), R 1 and R 2 are connected to each other to form a cyclic amine group having 3 to 6 carbon atoms together with the nitrogen atom to which R 1 and R 2 are bonded.
The organic group 13 precursor may be represented by the following formula (7).
≪ Formula 7 >
The organic group 13 precursor may be represented by the following formula (8).
(8)
Wherein L 1 and L 2 are each independently any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms and each of R 1 and R 2 independently represents an alkyl group having 1 to 6 carbon atoms , And a cycloalkyl group having 3 to 6 carbon atoms.
The organic group 13 precursor may be represented by the following formula (9).
≪ Formula 9 >
The organic group 13 precursor may be represented by the following formula (10).
≪ Formula 10 >
The organic Group 13 precursor may be represented by the following Formula 11.
≪ Formula 11 >
The organic Group 13 precursor may be represented by Formula 12 below.
≪ Formula 12 >
Wherein R 1 and R 2 are connected to each other to form a cyclic amine group having 3 to 6 carbon atoms together with the nitrogen atom bonded to R 1 and R 2 .
The organic group 13 precursor may be represented by the following formula (13).
≪ Formula 13 >
The thin film deposition method according to an embodiment of the present invention includes a deposition process for depositing a thin film on a substrate using the organic Group 13 precursor.
The deposition process may be performed by an atomic layer deposition (ALD) process or a chemical vapor deposition (CVD) process.
The chemical vapor deposition (CVD) may include metal organic chemical vapor deposition (MOCVD).
The deposition process includes: a loading step of loading a substrate into a chamber; A heating step of heating a substrate loaded in the chamber; A supply step of supplying the organic group 13 precursor into the chamber in which the substrate is loaded; A compound layer forming step of forming an organic Group 13 compound layer by adsorbing the organic Group 13 precursor on the substrate; And forming a film containing the Group 13 element on the substrate by applying a thermal energy, a plasma, or an electrical bias to the substrate.
The heating step may heat the substrate to a temperature ranging from 50 to 800 ° C.
In the supplying step, the organic group 13 precursor may be heated to a temperature ranging from 20 to 100 ° C and supplied onto the substrate.
The supplying step may be performed by mixing at least one carrier gas selected from argon (Ar), nitrogen (N 2 ), helium (He) and hydrogen and the organic group 13 precursor onto the substrate.
The Group 13 element-containing film may be an aluminum film or a gallium film.
The supplying step may further include a reactive gas supplying step of supplying at least one reaction gas selected from among water vapor (H 2 O), oxygen (O 2 ), and ozone (O 3 ) onto the substrate.
The Group 13 element-containing film may be an aluminum oxide film or a gallium oxide film.
The supplying step may further include a reactive gas supplying step of supplying at least one reaction gas selected from ammonia (NH 3 ), hydrazine (N 2 H 4 ), nitrogen dioxide (NO 2 ) and nitrogen (N 2 ) can do.
The Group 13 element-containing film may be an aluminum nitride film or a gallium nitride film.
The effect of the organic group 13 precursor according to one embodiment of the present invention and the thin film deposition using the Group 13 precursor is as follows.
The organic group 13 precursor according to an embodiment of the present invention has a small molecular size but has a high boiling point and therefore exists in a liquid state at room temperature and is excellent in thermal stability.
The organic group 13 precursor according to an embodiment of the present invention exhibits a strong affinity with a silicon substrate and a metal atom because it contains a nitrogen atom having an unshared electron pair and an organic group 13 atom in one molecular structure.
When a Group 13 element-containing film is deposited using the organic Group 13 precursor according to an embodiment of the present invention, since it has a decomposition temperature similar to the decomposition temperature of the metal precursor compound serving as a metal source, window can be narrowed.
Since the organic group 13 precursor according to an embodiment of the present invention has non-explosive and non-combustible properties, it is easy to maintain, repair, and maintain the equipment when depositing a film containing a Group 13 element.
When the Group 13 element-containing film is deposited using the organic Group 13 precursor according to one embodiment of the present invention, the number of molecules of the organic Group 13 precursor adsorbed per unit area of the lower structure increases, thereby improving the deposition density and the deposition uniformity. Thus, the step coverage of the Group 13 element containing film is improved.
The organic group 13 precursor according to an embodiment of the present invention has a vapor pressure lower than that of trimethylaluminum (TMA) in the vapor deposition precursor, so that the deposition rate can be controlled in the thin film deposition.
Accordingly, the organic Group 13 element-containing film can be effectively deposited using the organic Group 13 precursor according to one embodiment of the present invention.
1 is a graph showing the results of thermal analysis of diethylaminodiethylaluminum.
2 is a graph showing the results of a thermal analysis test of dimethylaminodiethylaluminum.
3 is a graph showing the results of a thermal analysis test of ethyl methyl amino diethyl aluminum.
4 is a graph showing the results of thermal analysis of pyrrolidinodiethylaluminum.
5 is a graph showing the results of thermal analysis of dimethylaminoethylgallium.
6 is a graph showing the results of thermal analysis of pyrrolidino diethyl gallium.
7 is a graph showing the results of ICP-AES component analysis of an aluminum-containing film deposited using diethylaminodiethyl aluminum.
8 is a graph showing the results of ASE component analysis of an aluminum-containing film deposited using diethylaminodiethyl aluminum.
9 is a graph showing the growth rate per cycle with respect to the process temperature of an aluminum-containing film deposited using diethylaminodiethylaluminum.
10 is a graph showing the film thickness per cycle of an aluminum-containing film deposited using diethylaminodiethyl aluminum.
11 is a graph showing the results of ICP-AES component analysis of an aluminum-containing film deposited using dimethylamino diethyl aluminum.
12 is a graph showing the results of ASE component analysis of an aluminum-containing film deposited using dimethylamino diethyl aluminum.
13 is a graph showing the growth rate per cycle versus processing temperature of an aluminum containing film deposited using dimethylamino diethyl aluminum.
14 is a graph showing the film thickness per period of an aluminum-containing film deposited using dimethylamino diethyl aluminum.
15 is a graph showing the results of ICP-AES component analysis of an aluminum-containing film deposited using pyrrolidinodiethyl aluminum.
16 is a graph showing the results of ASE component analysis of an aluminum-containing film deposited using pyrrolidinodiethyl aluminum.
17 is a graph showing the film thickness of a film containing aluminum deposited using pyrrolidinodiethyl aluminum.
The present invention relates to an organic Group 13 precursor and a thin film deposition method using the Group 13 precursor and an embodiment of the present invention. The embodiments of the present invention can be modified in various forms, and the scope of the present invention should not be construed as being limited to the embodiments described below.
The organic group 13 precursor according to one embodiment of the present invention is expressed by the following formula (1).
≪
Wherein M is any one selected from the metal elements belonging to Group 13 elements in the periodic table, L 1 and L 2 are each independently selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms And R 1 and R 2 are each independently any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms.
In general, trimethylaluminum (TMA) is widely used as a precursor for forming an aluminum-containing film. Since trimethyl aluminum (TMA) is used in various fields besides thin film deposition, there is an advantage that it is easy to supply and supply raw materials, has a very high vapor pressure, and is thermally stable. However, since trimethyl aluminum (TMA) has a very high vapor pressure, the deposition rate of the thin film can not be controlled, and even if only a very small amount of air is exposed to air, there is a risk that a fire occurs due to spontaneous ignition. In addition, since trimethyl aluminum (TMA) is a compound composed only of aluminum and carbon, impurity carbon is formed when the thin film is deposited, and the quality of the thin film is deteriorated.
The present invention seeks to provide an organic Group 13 precursor that can complement the disadvantages of this trimethylaluminum (TMA) and effectively deposit an aluminum-containing film.
The aluminum thin film deposition precursor according to one embodiment of the present invention is represented by the following formula (2).
(2)
Wherein L 1 and L 2 are each independently any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms and R 1 and R 2 each independently represent an alkyl group having 1 to 6 carbon atoms , And a cycloalkyl group having 3 to 6 carbon atoms.
The substituents L 1 , L 2 , R 1 and R 2 of the aluminum thin film deposition precursor represented by
(3)
The substituents L 1 and L 2 of the aluminum thin film deposition precursor represented by the
≪ Formula 4 >
The substituents L 1 , L 2 and R 1 of the aluminum thin film deposition precursor represented by the
≪ Formula 5 >
Wherein the <
(6)
The substituents L 1 and L 2 of the aluminum thin film deposition precursor represented by Formula 6 may be an alkyl group having 2 carbon atoms, and R 1 and R 2 may be the same or different from each other, together with the nitrogen atom bonded to R 1 and R 2 , To form a cyclic amine group. This is expressed by the following formula (7).
≪ Formula 7 >
The present invention also provides an organic group 13 precursor capable of effectively depositing a gallium-containing film.
The gallium thin film deposition precursor according to an embodiment of the present invention is represented by the following formula (8).
(8)
Wherein L 1 and L 2 are each independently any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms and each of R 1 and R 2 independently represents an alkyl group having 1 to 6 carbon atoms , And a cycloalkyl group having 3 to 6 carbon atoms.
The substituents L 1 , L 2 , R 1 and R 2 of the precursor of the gallium thin film represented by the formula (8) may be an alkyl group having 2 carbon atoms, which is represented by the following formula (9).
≪ Formula 9 >
The substituents L 1 and L 2 of the precursor of the gallium thin film represented by the
≪ Formula 10 >
The substituents L 1 , L 2 and R 1 of the precursor of the gallium thin film represented by the
≪ Formula 11 >
Wherein the <
≪ Formula 12 >
The substituents L 1 and L 2 of the gallium film thin film deposition precursor represented by Formula 12 may be an alkyl group having 2 carbon atoms, and R 1 and R 2 may be the same or different from each other, together with the nitrogen atom bonded to R 1 and R 2 , To form a cyclic amine group. This is represented by the following formula (13).
≪ Formula 13 >
The organic group 13 precursor according to one embodiment of the present invention will be described in more detail with reference to the following experimental examples. The following experimental examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited to the following experimental examples.
In the following examples, all the synthesis steps were performed using the standard vacuum line Schlenk technique and all syntheses were carried out under a nitrogen or argon gas atmosphere. Structural analysis of the synthesized compound was carried out using JEOL JNM-
In the following Experimental Examples, a differential scanning calorimetry (DSC) test was conducted using a thermal analyzer (TA Instruments Co., Ltd., model: TA-Q 600) in a differential scanning calorimetry mode, The analyzer was run in thermogravimetric analysis mode.
Experimental Example 1: (diethylamino) diethylalluminum, (CH 3 CH 2 ) 2 Al (N (CH 3 CH 2 ) 2 )
200 mL of anhydrous toluene and 10.0 g (0.088 mol) of triethyl aluminum were added to a 500 mL round-bottomed flask. 6.41 g (0.088 mol) of DEA (diethylamine) was added slowly using a dropping funnel while keeping the internal temperature of the round flask with branches at 0 ° C. When the DEA (diethylamine) addition was completed, the internal temperature of the flask was raised to 30 DEG C and further stirred for about 4 hours.
After completion of the stirring for 4 hours, the internal temperature was elevated to 110 DEG C and stirred for 30 hours. After stirring for 30 hours, the solvent was removed under reduced pressure, and the remaining yellow liquid was purified under reduced pressure to obtain 11 g of diethylamino diethylalluminum (yield: 80%).
Boiling point (b.p): 85 ° C at 0.8 torr
1 H-NMR (C 6 D 6): δ 2.68 [(CH 3 CH 2) 2 Al (N (CH 3 CH 2) 2), q, 4H]
1 H-NMR (C 6 D 6): δ 0.79 [(CH 3 CH 2) 2 Al (N (CH 3 CH 2) 2), t, 6H]
1 H-NMR (C 6 D 6): δ 0.15 [(CH 3 CH 2) 2 Al (N (CH 3 CH 2) 2), q, 4H]
1 H-NMR (C 6 D 6): δ 1.30 [(CH 3 CH 2) 2 Al (N (CH 3 CH 2) 2), t, 6H]
Experimental Example 2: (dimethylamino) diethylalluminum, (CH 3 CH 2 ) 2 Al (N (CH 3 ) 2 )
200 mL of anhydrous toluene and 10.0 g (0.088 mol) of TEA (triethyl aluminum) were added to a 500 mL round-bottom flask. 3.95 g (0.088 mol) of DMA (dimethylamine) was slowly added slowly using a dropping funnel while keeping the internal temperature of the round flask with branches at 0 ° C. After the addition of dimethylamine (DMA) was completed, the internal temperature of the flask was raised to 30 DEG C and further stirred for about 4 hours.
When stirring for 4 hours was completed, the internal temperature was raised to 110 DEG C and stirring was continued for 30 hours. After stirring for 30 hours, the solvent was removed under reduced pressure, and the remaining yellow liquid was purified by vacuum filtration to obtain 9.05 g (yield: 80%) of yellow, dimethylamino diethylalluminum.
Boiling point (b.p): 65 ° C at 0.8 torr
1 H-NMR (C 6 D 6): δ 2.11 [(CH 3 CH 2) 2 Al (N (CH 3) 2), s, 6H]
1 H-NMR (C 6 D 6 ):? 0.10 [(CH 3 CH 2 ) 2 Al (N (CH 3 ) 2 )
1 H-NMR (C 6 D 6): δ 1.27 [(CH 3 CH 2) 2 Al (N (CH 3) 2), t, 6H]
Preparation of (ethylmethylamino) diethylalluminum, (CH 3 CH 2) 2 Al (N (CH 3 CH 2) (CH 3)): Example 3
200 mL of anhydrous toluene and 10.0 g (0.088 mol) of TEA (triethyl aluminum) were added to a 500 mL round-bottom flask. 3.95 g (0.088 mol) of EMA (ethylmethylamine) was slowly added slowly using a dropping funnel while keeping the internal temperature of the round flask with branches at 0 ° C. When the addition of EMA (ethylmethylamine) was completed, the internal temperature of the flask was raised to 30 DEG C and further stirred for about 4 hours.
When stirring for 4 hours was completed, the internal temperature was raised to 110 DEG C and stirring was continued for 30 hours. When stirring was completed for 30 hours, the solvent was removed under reduced pressure and the remaining yellow liquid was purified by vacuum filtration to obtain 10.03 g (yield: 80%) of yellow viscous liquid (ethylmethylamino) diethylalluminum.
Boiling point (b.p): 65 ° C at 0.8 torr
1 H-NMR (C 6 D 6 ):? 2.55 [(CH 3 CH 2 ) 2 Al (N (CH 3 CH 2 ) (CH 3 )
1 H-NMR (C 6 D 6 ):? 0.81 [(CH 3 CH 2 ) 2 Al (N (CH 3 CH 2 ) (CH 3 )
1 H-NMR (C 6 D 6 ):? 2.11 [(CH 3 CH 2 ) 2 Al (N (CH 3 CH 2 ) (CH 3 )
1 H-NMR (C 6 D 6 ):? 0.15 [(CH 3 CH 2 ) 2 Al (N (CH 3 CH 2 ) (CH 3 )
1 H-NMR (C 6 D 6 ):? 1.28 [(CH 3 CH 2 ) 2 Al (N (CH 3 CH 2 ) (CH 3 )
Preparation of (pyrrolidino) diethylalluminum, (CH 3 CH 2) 2 Al (NC 4 H 8): Experimental Example 4
200 mL of anhydrous toluene and 10.0 g (0.088 mol) of TEA (triethyl aluminum) were added to a 500 mL round-bottom flask. 6.23 g (0.088 mol) of Pyrrolidine was slowly added slowly using a dropping funnel while keeping the internal temperature of the round flask with branches at 0 占 폚. After the addition of pyrrolidine was completed, the temperature inside the flask was raised to 30 DEG C and further stirred for about 4 hours.
When stirring for 4 hours was completed, the internal temperature was raised to 110 DEG C and stirring was continued for 30 hours. After stirring for 30 hours was completed, the solvent was removed under reduced pressure, and the remaining yellow liquid was purified by vacuum filtration to obtain 10.88 g (yield: 80%) of yellow viscous liquid (pyrrolidino diethylalluminum).
Boiling point (bp): 110 ° C at 0.8 torr
1 H-NMR (C 6 D 6 ):? 2.65 [(CH 3 CH 2 ) 2 Al (NC 4 H 8 ), m, 4H]
1 H-NMR (C 6 D 6 ):? 1.34 [(CH 3 CH 2 ) 2 Al (NC 4 H 8 ), m, 4H]
1 H-NMR (C 6 D 6 ):? 0.12 [(CH 3 CH 2 ) 2 Al (NC 4 H 8 ), q, 4H]
1 H-NMR (C 6 D 6 ):? 1.28 [(CH 3 CH 2 ) 2 Al (NC 4 H 8 ), t, 6H]
Experimental Example 5: (dimethylamino) diethylgallium, ( CH 3 CH 2) 2 Synthesis of Ga (N (CH 3) 2 )
250 ml of mesitylene was added to a 500 ml round-bottomed flask according to
Boiling point (b.p): 100 ° C at 0.5 torr
1 H-NMR (C 6 D 6 ):? 2.230 [(CH 3 CH 2 ) 2 Ga (N (CH 3 ) 2 )
1 H-NMR (C 6 D 6): δ 1.26, 1.28, 1.30 [(CH 3 CH 2) 2 Ga (N (CH 3) 2), m, 6H]
1 H-NMR (C 6 D 6): δ 0.50, 0.52, 0.54, 0.56 [(CH 3 CH 2) 2 Ga (N (CH 3) 2), m, 4H]
<
Experimental Example 6: Synthesis of (pyrrolidino) diethylgallium, (CH 3 CH 2) 2 Ga (NC 4 H 8)
According to the following
Boiling point (b.p): 120 ° C at 0.8 torr
1 H-NMR (C 6 D 6): δ 2.70, 2.69, 2.68, 2.67 [(CH 3 CH 2) 2 Ga (NC 4 H 8), br, 2H]
1 H-NMR (C 6 D 6 ):? 1.37, 1.36, 1.35, 1.34 [(CH 3 CH 2 ) 2 Ga (NC 4 H 8 )
1 H-NMR (C 6 D 6 ):? 1.31, 1.29, 1.27 [(CH 3 CH 2 ) 2 Ga (NC 4 H 8 )
1 H-NMR (C 6 D 6 ):? 0.55, 0.53, 0.51, 0.49 [(CH 3 CH 2 ) 2 Ga (NC 4 H 8 )
<
Experimental Example 7: Thermal analysis test
The diethylaminoethyl aluminum of Experimental Example 1, the dimethyl amino diethyl aluminum of Experimental Example 2, the ethyl methyl amino diethyl aluminum of Experimental Example 3, the pyrrolidinodiethyl aluminum of Experimental Example 4, the dimethyl Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) tests were performed on aminodiethyl gallium and diethyl gallium pyrrolidinone of Experimental Example 6.
The differential scanning calorimetry (DSC) and thermogravimetric (TGA) test conditions are as follows.
Transfer gas: argon (Ar) gas,
Transfer gas flow rate: 100 cc / min,
Heating profile: Heating from 30 占 폚 to 350 占 폚 at a heating rate of 10 占 폚 / min,
Sample volume: 10 mg.
The results of the thermal analysis of the diethylaminodiethylaluminum of Experimental Example 1 are shown in Fig. 1 shows the DSC curve and the TGA curve obtained through the thermal analysis test in a single figure, the curve with the dotted line shows the result obtained from the DSC test, and the curve with the solid line The results obtained from the TGA test are shown. The pyrolysis temperature of the DSC test was specified as the temperature at which the heat flow decreased at the time of heating the DSC thermal curve, but suddenly rose again. As shown in FIG. 1, the pyrolysis temperature of diethylaminodiethyl aluminum is about 237.12 ° C., and the residue amount is about 1.613% of the initial weight. Therefore, the diethylaminodiethyl aluminum of the present invention is excellent in thermal stability and can be confirmed that the residue is small.
The results of the thermal analysis test of the dimethylamino diethyl aluminum of Experimental Example 2 are shown in Fig. FIG. 2 shows a DSC thermal curve and a TGA thermal curve obtained through the thermal analysis test results in a single figure, showing the results obtained from the DSC test of the thermal curve indicated by the dashed line, and the solid curve indicated by the solid line The results obtained from the TGA test are shown. The pyrolysis temperature of the DSC test was specified as the temperature at which the DSC heat curve suddenly rises again while the heat flow decreases at the time of temperature rise. As shown in FIG. 2, the thermal decomposition temperature of dimethylaminodiethyl aluminum is about 192.79 ° C., and the residue amount is about 2.100% of the initial weight. Therefore, it can be confirmed that the dimethylamino dicetyl aluminum of the present invention is excellent in heat stability and the residue is small.
The results of the thermal analysis test of ethylmethylaminodiethylaluminum of Experimental Example 3 are shown in FIG. FIG. 3 is a graph showing the DSC thermal curve and the TGA thermal curve obtained from the results of the thermal analysis test in a single figure, the thermal curve indicated by the dotted line indicates the results obtained from the DSC test, and the thermal curve indicated by the solid line The results obtained from the TGA test are shown. The pyrolysis temperature of the DSC test was specified as the temperature at which the heat flow decreased at the time of heating the DSC thermal curve, but suddenly rose again. As shown in FIG. 3, the pyrolysis temperature of ethylmethylaminodiethyl aluminum is about 217.04 ° C., and the residue amount is about 1.218% of the initial weight. Therefore, the ethyl methyl amino diethyl aluminum of the present invention is excellent in heat stability and can be confirmed that the residue is small.
The results of the thermal analysis test of the pyrrolidino diethylaluminum of Experimental Example 4 are shown in Fig. FIG. 4 is a graph showing the DSC heat curve and the TGA heat curve obtained through the results of the thermal analysis test in a single drawing. The heat curve indicated by the dotted line indicates the result obtained from the DSC test, The results obtained from the TGA test are shown. The pyrolysis temperature of the DSC test was specified as the temperature at which the heat flow decreased at the time of heating the DSC thermal curve, but suddenly rose again. As shown in FIG. 4, the thermal decomposition temperature of the pyrrolidinodiethyl aluminum is about 217.04 ° C., and the residue amount is about 1.218% of the initial weight. Therefore, the pyrrolidino diethyl aluminum of the present invention is excellent in thermal stability and can be confirmed that the residue is small.
The results of the thermal analysis test of dimethylamino diethyl gallium of Experimental Example 5 are shown in Fig. FIG. 5 shows the DSC thermal curve and the TGA thermal curve obtained through the results of the thermal analysis test in a single figure. The heat curve indicated by the green solid line shows the result obtained from the DSC test, and the column indicated by the blue solid line The curve shows the results obtained from the TGA test. The pyrolysis temperature of the DSC test was specified as the temperature at which the heat flow decreased at the time of heating the DSC thermal curve, but suddenly rose again. As shown in Fig. 5, the thermal decomposition temperature of dimethylaminodiethyl gallium was found to be 198.74 占 폚, and T1 / 2 was found to be 178.83 占 폚. Also, it can be confirmed that the amount of residue remaining after raising the temperature to 350 캜 is about 3.2% of the initial weight. Therefore, the dimethylaminoethylgallium of the present invention is excellent in thermal stability and can be confirmed that the residue is small.
The results of the thermal analysis test of the diethyl gallium pyrrolidone of Experimental Example 6 are shown in Fig. FIG. 6 is a graph showing the DSC heat curve and the TGA thermal curve obtained through the results of the thermal analysis test in a single figure. The heat curve indicated by the green solid line shows the result obtained from the DSC test, The curve shows the results obtained from the TGA test. The pyrolysis temperature of the DSC test was specified as the temperature at which the heat flow decreased at the time of heating the DSC thermal curve, but suddenly rose again. As shown in FIG. 6, pyrolytic diethyl gallium was found to have a thermal decomposition temperature of 229.28 ° C and a T1 / 2 of 251.31 ° C. Also, it can be confirmed that the amount of residue remaining after raising the temperature to 350 캜 is about 3.466% of the initial weight. Therefore, the pyrrolidino diethyl gallium of the present invention is excellent in thermal stability and can be confirmed that the residue is small.
As described above, the organic group 13 precursor according to an embodiment of the present invention has a small molecular size but has a high boiling point, and therefore is present in a liquid state at room temperature and has excellent thermal stability. In addition, since it contains a nitrogen atom having a non-covalent electron pair and an aluminum or gallium atom in one molecular structure, it exhibits a strong affinity with a silicon substrate and a metal atom.
A thin film deposition method according to another embodiment of the present invention includes a deposition process for depositing an aluminum-containing film or a gallium-containing film on a substrate using the aforementioned organic group 13 precursor.
The deposition process may be performed by an atomic layer deposition (ALD) process or a chemical vapor deposition (CVD) process, and the chemical vapor deposition (CVD) Chemical Vapor Deposition, MOCVD).
The deposition process includes a loading step (S100) for loading a substrate into a chamber for providing a space in which a process for the substrate is performed, a heating step (S200) for heating a substrate loaded inside the chamber, (S300) for supplying an organic group 13 precursor according to an embodiment of the present invention to the inside of the compound layer, a compound layer for forming an organic aluminum compound layer or an organic gallium compound layer by adsorbing the supplied organic group 13 precursor on a substrate (S500) for forming an aluminum-containing film or a gallium-containing film by applying a thermal energy, a plasma or an electrical bias to the substrate on which the organic aluminum compound layer or the organic gallium compound layer is formed.
In the heating step (S200), the substrate can be heated to a temperature ranging from 50 to 800 ° C. In the supplying step (S300), the organic group 13 precursor can be heated to a temperature ranging from 20 to 100 ° C to be supplied onto the substrate.
In the supplying step S300, an organic group 13 precursor according to an embodiment of the present invention may be mixed with at least one carrier gas selected from argon (Ar), nitrogen (N 2 ), helium (He) have. When only a mixture of the organic group 13 precursor and the carrier gas according to an embodiment of the present invention is supplied onto the substrate and an evaporation process is performed, an aluminum film or a gallium film is deposited on the substrate.
In the supplying step S300, an organic group 13 precursor according to an embodiment of the present invention is supplied onto a substrate and an oxygen-based reaction gas such as water vapor (H 2 O), oxygen (O 2 ) and ozone (O 3 ) Can be supplied onto the substrate. The oxygen-based reaction gas may be supplied onto the substrate together with the organic Group 13 precursor according to an embodiment of the present invention, and may be supplied onto the substrate separately from the organic Group 13 precursor according to an embodiment of the present invention. When the oxygen-based reaction gas is supplied onto the substrate to perform the deposition process, a metal aluminum oxide film or a gallium oxide film such as an aluminum oxide film, a hafnium aluminum oxide film, a zirconium aluminum oxide film and a titanium aluminum oxide film, , A zirconium gallium oxide film, a titanium gallium oxide film, or the like may be formed.
Supplying an organic Group 13 precursor according to one embodiment of the present invention in the supply step (S300) onto the substrate, and ammonia (NH 3), hydrazine (N 2 H 4), nitrogen dioxide (NO 2) and nitrogen (N 2) Or the like can be supplied onto the substrate. The nitrogen-based reaction gas may be supplied onto the substrate together with the organic group 13 precursor according to an embodiment of the present invention, or may be supplied onto the substrate separately from the organic group 13 precursor according to an embodiment of the present invention. A metal aluminum nitride film or a gallium nitride film such as an aluminum nitride film, a hafnium aluminum nitride film, a zirconium aluminum nitride film, and a titanium aluminum nitride film, a hafnium gallium nitride film, , A gallium nitride film such as a zirconium gallium nitride film and a titanium gallium nitride film may be formed.
In the supplying step S300, the organic Group 13 precursor according to an exemplary embodiment of the present invention may be prepared by a bubbling method, a vapor phase mass flow controller method, a direct liquid injection (DLI) And may be supplied onto a substrate by a liquid transporting method or the like for dissolving in an organic solvent and transporting it, but it is not necessarily limited to these methods.
A first purge gas selected from an inert gas such as argon (Ar), nitrogen (N 2 ), and helium (He) is supplied into the chamber after the compound layer formation step (S400) A first purge step (S410) of removing the precursor may be performed. In the first purge step (S410), the first purge gas may be supplied into the chamber for less than one minute.
After the film formation step (S500), argon (Ar), nitrogen (N 2) and helium (He) and the second purge gas is selected from inert gas, such as feed into the chamber the second purge to remove excess reaction gas and generating a by-product Step S510 may be performed and in the second purge step S510, the second purge gas may be introduced into the chamber for less than one minute.
The thin film deposition method using an organic group 13 precursor according to an embodiment of the present invention will be described in detail with reference to the following examples. The following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited to the following examples.
≪ Example 1 >
Deposition of aluminum containing films using diethylaminodiethyl aluminum compounds as precursors and analysis of deposited aluminum containing films:
An aluminum-containing film deposition experiment was performed on the substrate using the diethylaminodiethyl aluminum compound obtained in the above <Experimental Example 1> as a precursor. A silicon (Si) wafer was used as the substrate, and the deposition process was carried out at a process temperature of 400 DEG C in the chamber. The diethylaminodiethyl aluminum compound was vaporized in a container made of stainless steel, and the vaporization temperature of the vaporizer was set at 175 ° C. Argon (Ar) gas having a flow rate of 250 sccm was used as the carrier gas, and the diethylaminodiethyl aluminum compound was fed at a feed rate of 0.02 g per minute using LMF (Liguid Flow Meter). The temperature of the feed line feeding the diethylamino diethyl aluminum compound into the chamber was maintained in the temperature range of 180-185 占 폚.
The process pressure in the chamber was adjusted to 0.3 torr and the process conditions were controlled such that the diethylaminodiethyl aluminum compound gas alternately contacts the substrate with O 2 . In the deposition process, a cycle of supplying diethylaminodiethyl aluminum compound gas, 1 second of argon (Ar) gas, 0.2 second of O 2 gas supply and plasma, and 1 second of argon (Ar) gas was used for 1 second. The aluminum-containing film deposited by the deposition process was confirmed by ICP-AES and ASE component analysis.
FIG. 7 is a graph showing the results of ICP-AES component analysis of the aluminum-containing film deposited by the deposition process, and FIG. 8 is a graph showing the results of the ASE component analysis of the aluminum-containing film deposited by the deposition process. As shown in FIGS. 7 and 8, it can be confirmed that the residual carbon (C) is not present in the aluminum-containing film deposited by the deposition process. In addition, it was confirmed that the atomic percent ratio of Al and O was Al: O = 2: 3, confirming that aluminum oxide film (Al 2 O 3 ) was formed.
FIG. 9 is a graph showing the growth rate per cycle with respect to the process temperature of the aluminum-containing film deposited by the deposition process, and FIG. 10 is a graph showing the film thickness per period of the aluminum-containing film deposited by the deposition process. As shown in FIG. 9, the growth per cycle (GPC) in the temperature range of 350 to 500 ° C. is 0.75 to 0.8 Å. Since the growth rate (GPC) of trimethyl aluminum (TMA) per cycle is about 1.0 Å in the same temperature range, the aluminum-containing film deposited by the thin film deposition method according to one embodiment of the present invention is excellent in the case of using trimethyl aluminum It can be confirmed that the growth rate per cycle (GPC) is low. As shown in FIG. 10, it can be seen that the aluminum-containing film thickness deposited by the deposition process increases linearly as the deposition cycle progresses. Therefore, the aluminum-containing film deposited by the thin film deposition method according to an embodiment of the present invention can easily control the thickness of the thin film according to the adjustment of the deposition cycle.
≪ Example 2 >
Deposition of an aluminum-containing film using a dimethylamino diethyl aluminum compound as a precursor and analysis of the deposited aluminum-containing film:
An aluminum-containing film deposition experiment was performed on a substrate using the dimethylamino diethyl aluminum compound obtained in the above <Experimental Example 2> as a precursor. A silicon (Si) wafer was used as the substrate, and the deposition process was carried out at a process temperature of 400 DEG C in the chamber. The dimethylaminodiethyl aluminum compound was vaporized in a container made of stainless steel, and the vaporization temperature of the vaporizer was set at 130 ° C. Argon (Ar) gas having a flow rate of 250 sccm was used as a carrier gas, and the dimethylamino diethyl aluminum compound was fed at a feed rate of 0.02 g per minute using LMF (Liguid Flow Meter). The temperature of the feed pipe for feeding the dimethylamino diethyl aluminum compound into the chamber was maintained in the temperature range of 135-140 캜.
The process pressure in the chamber was adjusted to 0.3 torr and the process conditions were controlled such that the dimethylaminodiethyl aluminum compound gas alternately contacts the substrate with O 2 . In the deposition process, a cycle of supplying dimethylaminodiethyl aluminum compound gas, 1 second of argon (Ar) gas, 1 second of O 2 gas supply and plasma, and 1 second of argon (Ar) gas was used for 0.8 seconds. The aluminum-containing film deposited by the deposition process was confirmed by ICP-AES and ASE component analysis.
FIG. 11 is a graph showing the results of ICP-AES component analysis of the aluminum-containing film deposited by the deposition process, and FIG. 12 is a graph showing the results of the ASE component analysis of the aluminum-containing film deposited by the deposition process. As shown in FIGS. 11 and 12, it can be confirmed that the residual carbon (C) is not present in the aluminum-containing film deposited by the deposition process. In addition, it was confirmed that the atomic percent ratio of Al and O was Al: O = 2: 3, confirming that aluminum oxide film (Al 2 O 3 ) was formed.
FIG. 13 is a graph showing the growth rate per cycle with respect to the process temperature of the aluminum-containing film deposited by the deposition process, and FIG. 14 is a graph showing the film thickness per cycle of the aluminum-containing film deposited by the deposition process. As shown in FIG. 13, the growth per cycle (GPC) is in the range of 0.75 to 0.8 Å in a temperature range of 250 to 500 ° C. Since the growth rate (GPC) of trimethyl aluminum (TMA) per cycle is about 1.0 Å in the same temperature range, the aluminum-containing film deposited by the thin film deposition method according to one embodiment of the present invention is excellent in the case of using trimethyl aluminum It can be confirmed that the growth rate per cycle (GPC) is low. As shown in FIG. 14, it can be seen that the aluminum-containing film thickness deposited by the deposition process increases linearly as the deposition cycle progresses. Therefore, the aluminum-containing film deposited by the thin film deposition method according to an embodiment of the present invention can easily control the thickness of the thin film according to the adjustment of the deposition cycle.
≪ Example 3 >
Deposition of an aluminum containing film using a pyridridino diethyl aluminum compound as a precursor and analysis of the deposited aluminum containing film:
An aluminum-containing film deposition experiment was performed on the substrate using the pyridridino diethylaluminum compound obtained in Experimental Example 4 as a precursor. A silicon (Si) wafer was used as the substrate, and the deposition process was carried out at a process temperature of 400 DEG C in the chamber. The pyrrolidino diethyl aluminum compound was vaporized in a container made of stainless steel, and the vaporization temperature of the vaporizer was set at 175 ° C. Argon (Ar) gas having a flow rate of 250 sccm was used as a carrier gas, and the pyrrolidino diethyl aluminum compound was fed at a feed rate of 0.02 g per minute using LMF (Liguid Flow Meter). The temperature of the feed line to feed the pyrrolidino diethyl aluminum compound into the chamber was maintained in the temperature range of 180 to 185 占 폚.
The process pressure in the chamber was adjusted to 0.3 torr, and the process conditions were controlled such that the pyrrolidino diethyl aluminum compound gas alternately contacts the substrate with O 2 . In the deposition process, a period of supplying 0.6 g of pyrrolidino diethyl aluminum compound gas, 2 seconds of argon (Ar) gas supply, 1 second of O 2 gas supply and plasma, and 0.5 second of argon (Ar) gas was used. The aluminum-containing film deposited by the deposition process was confirmed by ICP-AES and ASE component analysis.
15 is a graph showing the results of the ICP-AES component analysis of the aluminum-containing film deposited by the deposition process, and FIG. 16 is a graph showing the results of the ASE component analysis of the aluminum-containing film deposited by the deposition process. As shown in FIG. 15 and FIG. 16, it can be confirmed that the residual carbon (C) is not present in the aluminum-containing film deposited by the deposition process. In addition, it was confirmed that the atomic percent ratio of Al and O was Al: O = 2: 3, confirming that aluminum oxide film (Al 2 O 3 ) was formed.
17 is a graph showing the film thickness of the aluminum-containing film deposited by the deposition process with respect to the process temperature based on 200 cycles. As shown in FIG. 17, the growth per cycle (GPC) is about 0.4 A in the temperature range of 350 to 450 ° C. Since the growth rate (GPC) of trimethyl aluminum (TMA) per cycle is about 1.0 Å in the same temperature range, the aluminum-containing film deposited by the thin film deposition method according to one embodiment of the present invention is excellent in the case of using trimethyl aluminum It can be confirmed that the growth rate per cycle (GPC) is low. Therefore, the aluminum-containing film deposited by the thin film deposition method according to an embodiment of the present invention can easily control the thickness of the thin film according to the adjustment of the deposition cycle.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, Therefore, the technical idea and scope of the claims set forth below are not limited to the embodiments.
Claims (25)
(6)
≪ Formula 12 >
Wherein L 1 and L 2 are each independently any one selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms and R 1 and R 2 are each independently a group selected from the group consisting of a carbon number A cycloalkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms, R 1 and R 2 are connected to each other to form a cyclic amine group having 3 to 6 carbon atoms together with a nitrogen atom bonded to R 1 and R 2 .
Wherein the organic Group 13 precursor is represented by Formula 7 below.
≪ Formula 7 >
Wherein the organic Group 13 precursor is represented by Formula 13 below.
≪ Formula 13 >
The deposition process may include:
(ALD) process or a Chemical Vapor Deposition (CVD) process.
The chemical vapor deposition (CVD)
A method of depositing a thin film, the method comprising metal organic chemical vapor deposition (MOCVD).
The deposition process may include:
A loading step of loading a substrate inside the chamber;
A heating step of heating a substrate loaded in the chamber;
A supply step of supplying the organic group 13 precursor into the chamber in which the substrate is loaded;
A compound layer forming step of forming an organic Group 13 compound layer by adsorbing the organic Group 13 precursor on the substrate; And
Applying a thermal energy, a plasma, or an electrical bias to the substrate to form the film containing the Group 13 element on the substrate.
In the heating step,
Wherein the substrate is heated to a temperature in the range of 50 to 800 占 폚.
Wherein the supplying step comprises:
Wherein the organic Group 13 precursor is heated to a temperature ranging from 20 to 100 占 폚 and supplied onto the substrate.
Wherein the supplying step comprises:
Wherein at least one carrier gas selected from argon (Ar), nitrogen (N 2 ), helium (He) and hydrogen is mixed with the organic group 13 precursor and supplied onto the substrate.
Wherein the Group 13 element-containing film is an aluminum film or a gallium film.
Wherein the supplying step comprises:
Further comprising a reaction gas supplying step of supplying at least one reaction gas selected from among water vapor (H 2 O), oxygen (O 2 ) and ozone (O 3 ) onto the substrate.
Wherein the Group 13 element-containing film is an aluminum oxide film or a gallium oxide film.
Wherein the supplying step comprises:
Further comprising a reactive gas supplying step of supplying at least one reaction gas selected from ammonia (NH 3 ), hydrazine (N 2 H 4 ), nitrogen dioxide (NO 2 ) and nitrogen (N 2 ) onto the substrate .
Wherein the Group 13 element-containing film is an aluminum nitride film or a gallium nitride film.
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| KR102087858B1 (en) * | 2018-04-18 | 2020-03-12 | 주식회사 한솔케미칼 | Precursor compound for atomic layer deposition(ald), chemical vapor deposition(cvd) and ald/cvd deposition using the same |
| TW202026452A (en) | 2018-10-04 | 2020-07-16 | 日商Ａｄｅｋａ股份有限公司 | Thin film forming raw material for atomic layer deposition method, thin film forming raw material, method for producing thin film and compound |
| CN115279940B (en) * | 2020-02-24 | 2024-04-09 | Up化学株式会社 | Aluminum precursor compound, method for producing the same, and method for forming aluminum-containing film using the same |
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| KR100781543B1 (en) | 2006-07-26 | 2007-12-03 | 삼성전자주식회사 | Method of forming a metal oxide by atomic layer deposition |
| US20090253725A1 (en) | 2008-03-20 | 2009-10-08 | Takeda Pharmaceutical Company Limited | ACETYL CoA CARBOXYLASE INHIBITORS |
| US20130330936A1 (en) * | 2011-02-07 | 2013-12-12 | Technische Universiteit Eindhoven | METHOD OF DEPOSITION OF Al2O3/SiO2 STACKS, FROM ALUMINIUM AND SILICON PRECURSORS |
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| KR100781543B1 (en) | 2006-07-26 | 2007-12-03 | 삼성전자주식회사 | Method of forming a metal oxide by atomic layer deposition |
| US20090253725A1 (en) | 2008-03-20 | 2009-10-08 | Takeda Pharmaceutical Company Limited | ACETYL CoA CARBOXYLASE INHIBITORS |
| US20130330936A1 (en) * | 2011-02-07 | 2013-12-12 | Technische Universiteit Eindhoven | METHOD OF DEPOSITION OF Al2O3/SiO2 STACKS, FROM ALUMINIUM AND SILICON PRECURSORS |
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