US20150024607A1 - Organoaluminum materials for forming aluminum oxide layer from coating composition that contains organic solvent - Google Patents
Organoaluminum materials for forming aluminum oxide layer from coating composition that contains organic solvent Download PDFInfo
- Publication number
- US20150024607A1 US20150024607A1 US13/947,129 US201313947129A US2015024607A1 US 20150024607 A1 US20150024607 A1 US 20150024607A1 US 201313947129 A US201313947129 A US 201313947129A US 2015024607 A1 US2015024607 A1 US 2015024607A1
- Authority
- US
- United States
- Prior art keywords
- aluminum oxide
- substrate
- layer
- curing
- coating composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 29
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims description 50
- 239000003960 organic solvent Substances 0.000 title claims description 20
- 239000000463 material Substances 0.000 title claims description 12
- 239000000758 substrate Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims description 55
- 150000001875 compounds Chemical class 0.000 claims description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 7
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 5
- 238000004528 spin coating Methods 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 3
- 238000007764 slot die coating Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000010410 layer Substances 0.000 description 64
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 50
- 238000001723 curing Methods 0.000 description 42
- 239000003795 chemical substances by application Substances 0.000 description 36
- 239000003446 ligand Substances 0.000 description 31
- 239000000203 mixture Substances 0.000 description 26
- 229940116333 ethyl lactate Drugs 0.000 description 25
- 235000012431 wafers Nutrition 0.000 description 25
- 229910052782 aluminium Inorganic materials 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- -1 aluminum compound Chemical class 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 230000004580 weight loss Effects 0.000 description 9
- 229910052814 silicon oxide Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- 229920000265 Polyparaphenylene Polymers 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000002198 insoluble material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- YSAVZVORKRDODB-WDSKDSINSA-N diethyl tartrate Chemical compound CCOC(=O)[C@@H](O)[C@H](O)C(=O)OCC YSAVZVORKRDODB-WDSKDSINSA-N 0.000 description 5
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229920002120 photoresistant polymer Polymers 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000000429 assembly Methods 0.000 description 3
- 230000000712 assembly Effects 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000006117 anti-reflective coating Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229920002457 flexible plastic Polymers 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 description 1
- 0 *[Al](*)O[1*].CC(C)O[Al](OC(C)C)OC(C)C.[1*]O Chemical compound *[Al](*)O[1*].CC(C)O[Al](OC(C)C)OC(C)C.[1*]O 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- KZWUIMDNAXYFBU-UHFFFAOYSA-N CCOC(=O)C(C)O[Al](OC(C)C(=O)OCC)OC(C)C(=O)OCC Chemical compound CCOC(=O)C(C)O[Al](OC(C)C(=O)OCC)OC(C)C(=O)OCC KZWUIMDNAXYFBU-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XYVQFUJDGOBPQI-UHFFFAOYSA-N Methyl-2-hydoxyisobutyric acid Chemical compound COC(=O)C(C)(C)O XYVQFUJDGOBPQI-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000005259 measurement 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
- 150000002739 metals Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GJYXGIIWJFZCLN-UHFFFAOYSA-N octane-2,4-dione Chemical compound CCCCC(=O)CC(C)=O GJYXGIIWJFZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- KXFSUVJPEQYUGN-UHFFFAOYSA-N trimethyl(phenyl)silane Chemical compound C[Si](C)(C)C1=CC=CC=C1 KXFSUVJPEQYUGN-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02178—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing aluminium, e.g. Al2O3
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/88—Passivation; Containers; Encapsulations
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/873—Encapsulations
Definitions
- the present invention relates generally to the field of solution-borne organometallic compounds, and more particularly to the field of manufacturing coated substrates using such solution-borne organometallic compounds.
- Oxymetal layers are generally characterized as films containing a majority of inorganic domains with (—M—O—) n linkages (oxymetal domains), where M is a metal and n>1, and may also be composed of minor amounts of other elements, such as carbon. Layers composed of mixed domains, such as containing both oxymetal domains and metal nitride domains, may be used.
- Conventional oxymetal films may contain one or more metals, such as Hf, Zr, Ti, W, Al, Ta and Mo, depending on the particular application.
- the etch resistance of oxymetal domain-containing films depends, in part, on the particular metal used as well as the level of (—M—O—) n domains present in the film, with an increased level of such domains providing greater etch resistance.
- Barrier films used in OLED applications conventionally contain Al or Si, that is (—Al—O—) n or (—Si—O—) n domains, respectively, where n>1.
- Aluminum oxide-containing films are known to have reduced transport of oxygen (O 2 ), while silicon oxide-containing films are known to have reduced transport of moisture vapor. Any defects in such barrier films, such as pinholes, or any other defect causing incomplete coverage of the lower film presents a possible pathway for gas or vapor to access the lower film.
- Oxymetal films such as alumina and silica films, are conventionally applied by chemical vapor deposition (CVD) onto an electronic device substrate.
- CVD chemical vapor deposition
- International Pat. App. WO 2012/103390 discloses a stack having one or more oxide-containing barrier layers, such as aluminum oxide or silicon oxide layers, adjacent to a reactive inorganic layer on a flexible (plastic) substrate for reducing the transport of gas or vapor through the stack.
- the reactive inorganic layer functions to react with any gas or vapor that penetrates through the barrier layer.
- This patent application fails to suggest any suitable materials for forming such barrier layers, and focuses on conventional film deposition techniques, such as vapor deposition techniques.
- Spin-on techniques are widely used in electronic device manufacture and offer advantages over conventional vapor deposition methods of depositing films. For example, spin-on techniques can use existing equipment, can be completed within a few minutes, and can provide a uniform coating over a substrate.
- Conventional aluminum sources such as Al(Oi—Pr) 3 , suffer from very poor solubility in solvents conventionally used in electronic device manufacture as well as from high susceptibility to water/moisture.
- Such conventional aluminum sources typically form aluminum oxide particles upon exposure to moisture, such as the residual moisture found in common solvents. Such aluminum oxide particles pose problems in liquid dispensing systems and even if capable of being dispensed such particles pose defect issues during the manufacture of electronic devices.
- oligomer refers to dimers, trimers, tetramers and other relatively low molecular weight materials that are capable of further curing.
- Alkyl and alkoxy refer to linear, branched and cyclic alkyl and “alkoxy”, respectively.
- curing is meant any process that polymerizes or otherwise increases, such as by condensation, the molecular weight of a film or layer.
- the articles “a”, “an” and “the” refer to the singular and the plural. All numerical ranges are inclusive and combinable in any order, except where it is clear that such numerical ranges are constrained to add up to 100%.
- (C 4 -C 10 )hydrocarbyl refers to any hydrocarbon moiety comprising 4-10 carbon atoms. Such (C 4 -C 10 )hydrocarbyl moiety may be aromatic or aliphatic, and preferably is aliphatic.
- the present organoaluminum compounds may be prepared by a variety of procedures known in the art, and are typically prepared by a ligand exchange reaction between a starting aluminum compound of the formula Al((C 1 -C 6 )alkoxy) 3 and a suitable higher order ligand, such as HL 2 or an alkali or alkaline earth salt thereof such as K + ⁇ L2, where L 2 is as defined above.
- a suitable higher order ligand such as HL 2 or an alkali or alkaline earth salt thereof such as K + ⁇ L2, where L 2 is as defined above.
- the higher order ligand used in the ligand exchange reaction has the formula HL 2 , and more preferably has the formula HOR 1 , where R 1 is as defined above.
- the starting aluminum compound Al((C 1 -C 6 )alkoxy) 3 is combined with the higher order ligand and a suitable organic solvent in a flask.
- the mixture is then heated, typically to reflux, for a period of time to allow the desired ligand exchange to occur.
- 1, 2 or all 3 of the (C 1 -C 6 )alkoxy ligands on the starting aluminum compound may be exchanged with a corresponding number of higher order ligands.
- Suitable compounds useful as higher order ligands in the present invention include, but are not limited to: 2,4-octanedione; methyl glycolate; ethyl glycolate; ethyl lactate; 2-methyl-l-butanol; 4-methyl-2-pentanol; and diethyl tartrate.
- Preferred organic solvents are methyl glycolate; ethyl glycolate; ethyl lactate; and diethyl tartrate
- any suitable organic solvent may be used for such ligand exchange reaction, and preferably the organic solvent has the formula HOR 1 , where R 1 is as defined above.
- the higher order ligand is also used as the organic solvent for the ligand exchange reaction. In this way, a large excess of the higher order ligand is present, and typically all 3 of the (C 1 -C 6 )alkoxy ligands are replaced with higher order ligands, as indicated according to the following equation:
- the organoaluminum compound comprising the higher order ligand that is, Al(OR 1 ) 3 in the above equation, should be separated from such organic solvent and subsequently combined with a solvent having the formula HOR 1 .
- Preferred organic solvents for the ligand exchange reaction are those having the formula HOR 1 , where R 1 is a (C 4 -C 10 )hydrocarbyl moiety, which is preferably aliphatic.
- R 1 is a (C 4 -C 10 )hydrocarbyl moiety, which is preferably aliphatic.
- Such (C 4 -C 10 )hydrocarbyl moiety may optionally comprise one or more substituents selected from the group consisting of hydroxyl, carboxylic acid and (C 1 -C 6 )alkyl carboxylate, preferably hydroxyl and (C 1 -C 6 )alkyl carboxylate, more preferably hydroxyl and (C 1 -C 4 )alkyl carboxylate, and yet more preferably hydroxyl and (C 2 -C 4 )alkyl carboxylate.
- Preferred organic solvents are ⁇ -hydroxy esters. It is also preferred that the (C 4 -C 10 )hydrocarbyl moiety of R 1 be bound to the oxygen through a secondary carbon atom.
- Suitable organic solvents include, without limitation: methyl glycolate; ethyl glycolate; ethyl lactate; 2-methyl-1-butanol; 4-methyl-2-pentanol; and diethyl tartrate.
- Preferred organic solvents are methyl glycolate; ethyl glycolate; ethyl lactate; and diethyl tartrate.
- Coating compositions useful in the present method comprise an organoaluminum compound of the formula AlL 1 x L 2 y , as described above, and an organic solvent of the formula HOR 1 , also as described above.
- the reaction product may be used in the solvent without isolation.
- the coating composition is filtered before use to remove any insoluble materials that form during the ligand exchange reaction.
- the present coating compositions may optionally include one or more surface leveling agents (or surfactants) or binder polymers. While any suitable surfactant may be used, such surfactants are typically non-ionic. The amount of such surfactants useful in the present compositions is well-known to those skilled in the art, and typically is in the range of 0 to 2% by weight.
- a wide variety of binder polymers may be used, such as to provide improved coating quality or leveling over the substrate. Suitable binder polymers are disclosed in U.S. patent application Ser. No. 13/776,496.
- the present coating compositions may further comprise one or more curing agents to aid in the curing of the deposited organoaluminum film.
- exemplary curing agents include thermal acid generators (TAGs) and photoacid generators (PAGs).
- Preferred curing agents are thermal acid generators. The amounts of such curing agents are within the ability of those skilled in the art. Any suitable curing agent may be used in the present coating compositions.
- the present coating compositions are useful in forming an aluminum oxide layer on various substrates, such as electronic device substrates, packaging substrates, separations substrates, or any other substrate where a gas barrier may be used.
- substrates such as electronic device substrates, packaging substrates, separations substrates, or any other substrate where a gas barrier may be used.
- a wide variety of electronic device substrates may be used in the present invention, such as: packaging substrates such as multichip modules; flat panel display substrates, including flexible display substrates; integrated circuit substrates; photovoltaic device substrates; substrates for light emitting diodes (LEDs, including organic light emitting diodes or OLEDs); semiconductor wafers; polycrystalline silicon substrates; and the like.
- Such substrates are typically composed of one or more of silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold.
- Suitable substrates may be in the form of wafers such as those used in the manufacture of integrated circuits, optical sensors, flat panel displays, integrated optical circuits, and LEDs.
- the term “semiconductor wafer” is intended to encompass “an electronic device substrate,” “a semiconductor substrate,” “a semiconductor device,” and various packages for various levels of interconnection, including a single-chip wafer, multiple-chip wafer, packages for various levels, or other assemblies requiring solder connections.
- patterned wafers such as patterned silicon wafers, patterned sapphire wafers, and patterned gallium-arsenide wafers.
- Such wafers may be any suitable size.
- Preferred wafer diameters are 200 mm to 300 mm, although wafers having smaller and larger diameters may be suitably employed according to the present invention.
- the term “semiconductive substrates” includes any substrate having one or more semiconductor layers or structures which include active or operable portions of semiconductor devices.
- semiconductor substrate is defined to mean any construction comprising semiconductive material, including but not limited to bulk semiconductive material such as a semiconductive wafer, either alone or in assemblies comprising other materials thereon, and semiconductive material layers, either alone or in assemblies comprising other materials.
- a semiconductor device refers to a semiconductor substrate upon which at least one microelectronic device has been or is being batch fabricated.
- Preferred substrates are substrates for LEDs, and more preferably for OLEDs.
- flexible display substrates and photovoltaic device substrates are also preferred.
- a layer of the present coating compositions may be disposed on a substrate, such as an electronic device substrate, by any suitable means, such as spin-coating, spray coating, slot-die coating, doctor blading, curtain coating, roller coating, dip coating, and the like. Spin-coating, spray coating and slot-die coating are preferred.
- the present coating compositions are applied to an electronic device substrate which is spinning at a rate of 500 to 4000 rpm for a period of 15-90 seconds to obtain a desired layer of the organoaluminum compound on the substrate. It will be appreciated by those skilled in the art that the height of the organoaluminum compound layer may be adjusted by changing the spin speed, as well as the percentage solids in the coating composition.
- the layer is optionally baked at a relatively low temperature to remove any remaining solvent and other relatively volatile components to form a layer of the organoaluminum compound.
- the substrate is baked at a temperature of ⁇ 125° C., preferably from 60 to 125° C., and more preferably from 90 to 115° C.
- the baking time is typically from 10 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, and more preferably from 6 to 180 seconds.
- such baking step may be performed by heating the wafer on a hot plate.
- the organoaluminum compound layer is cured, such as in an oxygen-containing atmosphere, such as air.
- the curing step is conducted preferably on a hot plate-style apparatus, though oven curing may be used to obtain equivalent results.
- such curing is performed by heating the organoaluminum compound layer at a curing temperature of ⁇ 150° C., preferably 150 to 450° C., and more preferably from 200 to 400° C.
- the choice of final curing temperature depends mainly upon the desired curing rate, with higher curing temperatures requiring shorter curing times.
- the curing time may be from 10 seconds to 120 minutes.
- This curing step is performed in order to thermally decompose at least a portion of the organoaluminum compound, and preferably all of the organoaluminum compound, so that a hardmask layer containing oxyaluminum domains (aluminum oxide) having an (—M—O—) n linkage, where n>1, preferably n>2, more preferably n>5, yet more preferably n>10, and even more preferably n>25 are obtained.
- the amount of aluminum in the cured oxyaluminum domain-containing films may be up to 95 mol % (or even higher), and preferably from 50 to 95 mol %.
- Aluminum oxide layers formed from the present compositions contain oxy-aluminum domains, and may contain other domains, such as aluminum nitride domains, as well as optionally containing carbon, such as an amount of up to 5 mol % carbon.
- the organoaluminum compound layer should be heated to a temperature sufficient to activate the TAG and generate an acid.
- the temperature used to cure the organoaluminum compound layer to form the aluminum oxide-containing layer is sufficient to activate the TAG.
- the organoaluminum compound layer may be exposed to light of an appropriate wavelength or to an electron beam to generate the corresponding acid. Such exposure step may occur before, during or both before and during the step of curing the organoaluminum compound layer to form the aluminum oxide-containing film.
- the resulting aluminum oxide-containing films are resistant to stripping (being removed) by solvents conventionally used in the application of antireflective coatings and photoresists.
- the present organoaluminum oligomer layers are cured at temperatures ⁇ 350° C., the resulting aluminum oxide-containing films are also resistant to stripping by alkaline or solvent developers conventionally used in the development of imaged photoresist layers.
- the initial baking step may not be necessary if the final curing step is conducted in such a way that rapid evolution of the solvents and curing by-products is not allowed to disrupt the film quality.
- a ramped bake beginning at relatively low temperatures and then gradually increasing to the range of 250 to 400° C. can give acceptable results.
- Two stage curing processes facilitate uniform filling and planarization of pre-existing substrate surface topography.
- the conversion of the organoaluminum to aluminum oxide involves hydrolysis by moisture that is contained in the coating and/or adsorbed from the atmosphere during the deposition (casting) and curing processes. Therefore, the curing process is preferably carried out in air or in an atmosphere where moisture is present to facilitate complete conversion to aluminum oxide.
- the curing process can also be aided by exposure of the coating to ultraviolet radiation, preferably in a wavelength range of from about 200 to 400 nm The exposure process can be applied separately or in conjunction with a thermal curing process.
- the cured aluminum oxide-containing layer may suitably be used as a hardmask, dielectric layer, barrier layer or for any other suitable use in the manufacture of various devices.
- the cured aluminum oxide-containing layers of the present invention are particularly suitable for use as a barrier layer, such as an oxygen barrier, in the manufacture of LEDs, and preferably in the manufacture of OLEDs, or in packaging applications or as a low diffusion gas barrier in separations applications.
- the present aluminum oxide-containing layers may be subjected to further processing steps, such as patterning.
- Such further processing steps may require the application of one or more organic materials, such as photoresists and antireflective coatings, to the surface of the aluminum oxide-containing layer.
- Oxy-metal containing layers typically have a surface energy that is very different from that of subsequently applied organic layers. Such a mismatch of surface energy causes poor adhesion between the oxymetal hardmask layer and the subsequently applied organic layer. In the case of a subsequently applied photoresist layer, such mismatch in surface energy results in severe pattern collapse.
- the surface may optionally be treated with an appropriate surface treating agent.
- Surface treating compositions useful for treating the present aluminum oxide-containing films surface are those disclosed in U.S. patent application Ser. No. 13/745,752 and comprise an organic solvent and a surface treating agent, where the surface treating agent comprises one or more surface treating moieties.
- the surface treating composition may further comprise one or more additives, such as thermal acid generators, photoacid generators, antioxidants, dyes, contrast agents, and the like.
- additives such as thermal acid generators, photoacid generators, antioxidants, dyes, contrast agents, and the like.
- organic solvents may suitably be used, such as, but are not limited to, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, lactones, esters, glycols, glycol ethers, and mixtures thereof.
- organic solvents include, without limitation, toluene, xylene, mesitylene, alkylnaphthalenes, 2-methyl-1-butanol, 4-methyl-2-pentanol, gamma-butyrolactone, ethyl lactate, 2-hydroxyisobutyric acid methyl ester, propylene glycol methyl ether acetate, and propylene glycol methyl ether.
- Suitable solvents have a relatively higher vapor pressure than the surface treating agent, such that the solvent may be removed from the surface of the film leaving behind the surface treating agent. It is preferred that the organic solvents do not have free carboxylic acid groups or sulfonic acid groups.
- surface treating agents may be used in the surface treating compositions and may be polymeric or non-polymeric, and comprise one or more surface treating moieties.
- Exemplary surface treating moieties include hydroxyl (—OH), thiol (—SH), carboxyl (—CO 2 H), betadiketo (—C(O)—CH 2 —C(O)—), protected carboxyl, and protected hydroxyl groups.
- amino groups will work, it is preferred that the surface treating agents are free of amino groups, and preferably free of nitrogen, as such groups may adversely affect the function of subsequently applied coatings such as chemically amplified photoresists.
- Protected carboxyl groups and protected hydroxyl groups are any groups which are cleavable under certain conditions to yield a carboxyl group or hydroxyl group, respectively. Such protected carboxyl groups and protected hydroxyl groups are well-known in the art. When the surface treating agent comprises one or more protected hydroxyl groups, it is preferred that a TAG or PAG be used in the surface treating composition.
- the present organoaluminum compound coating compositions may further comprise a surface treating agent having a surface energy of 20 to 40 erg/cm 2 and comprising a surface treating moiety chosen from hydroxyl, protected hydroxyl, protected carboxyl, and mixtures thereof, such as those described in copending U.S. patent application Ser. No. 13/745,753.
- a minimum of one surface treating moiety per surface treating agent molecule is required.
- the surface treating agent When added to the organoaluminum coating compositions, the surface treating agent is substantially free of un-protected carboxylic acid groups (that is, the surface treating agent comprises ⁇ 0.5 mol % un-protected or “free” carboxylic acid groups). In addition to the surface treating moiety, the surface treating agent also comprises one or more relatively more hydrophobic moieties, such as C 3-20 alkyl groups and C 6-20 aryl groups.
- a branched or cyclic alkyl group is relatively more hydrophobic than the corresponding linear alkyl group, and that increasing the branching or cyclic nature of such a group helps lower the surface energy of the surface treating agent.
- alkyl and aryl groups of increasing carbon chain length also lower the surface energy of the surface treating agent.
- the surface treating agent migrates toward the surface of the forming film during deposition of the coating compositions and/or during any subsequent solvent removal step. It is further believed that the relatively lower surface energy of the surface treating agent helps drive the surface treating agent to the air interface. It will be appreciated by those skilled in the art that such migration of the surface treating agent should substantially occur before the complete curing of the aluminum oxide-containing film. The formation of a cured aluminum oxide-containing film substantially prohibits migration of the surface treating agent.
- the temperature used to cure the organoaluminum compound layer should be selected such that the surface treating agent does not substantially decompose. If higher curing temperatures are required, then more thermally stable surface treating agents, such as vinylaryl polymers such as hydroxystyrene polymers and polyhedral oligosilsesquioxane polymers may be used.
- surrogate measurements such as water contact angles
- water contact angles are typically used.
- the determination of water contact angles is well-known, and a preferred method uses using a Kruss drop shape analyzer Model 100, using deionized (“DI”) water and a 2.5 ⁇ L drop size.
- Oxy-metal containing layers such as aluminum oxide-containing layers, typically have a water contact angle of ⁇ 50°, such as from 35 to 45°.
- the aluminum oxide-containing film surface typically has a water contact angle of ⁇ 55°, such as from 55 to 70°.
- the aluminum oxide-containing film surface has a surface energy that substantially matches that of a subsequently applied organic layer, that is, the surface energy of the treated aluminum oxide-containing layer should be within 20% of the surface energy of a subsequently applied organic layer. Subsequent processing steps involving organic layers applied over the aluminum oxide-containing layer will have fewer defects as compared to aluminum oxide-containing films without such surface treatment.
- Weight Loss Method Approximately 0.1 g of an obtained organoaluminum compound in solution was weighed into a tared aluminum pan. Approximately 0.5 g of the solvent used to form the organoaluminum compound (ethyl lactate) was added to the aluminum pan to dilute the test solution to make it cover the aluminum pan more evenly. The aluminum pan was heated in a thermal oven at approximately 110° C. for 15 minutes. After the aluminum pan cooled to room temperature, the weight of the aluminum pan with dried solid film was determined, and the percentage solid content was calculated.
- the solvent used to form the organoaluminum compound ethyl lactate
- the solution was then filtered through a 1.0 ⁇ m PFPE filter to remove any insoluble materials, and then filtered through a 0.2 ⁇ m PFPE filter.
- the filtered solution was found to contain ca. 8.8% solids using the weight loss method described in Example 1.
- Example 2 was repeated except that 0.2 g (0.57 equivalents) of DI water was used. After filtering, the solution was found to contain ca. 7.8% solids using the weight loss method described in Example 1.
- Example 2 The procedure of Example 2 was repeated except that 0.5 g (1.42 equivalents) of DI water was used. After filtration, the solution was found to contain ca. 6.7% solids using the weight loss method of Example 1.
- reaction mixture was then heated to reflux temperature again and held at reflux for 2 hours, after which heating was stopped and the reaction mixture was allowed to cool naturally to room temperature.
- the reaction mixture solution was then filtered through a 1.0 ⁇ m PFPE filter to remove any insoluble materials, and then filtered through a 0.2 ⁇ m PFPE filter. After filtration, the solution was found to contain ca. 7.9% solids using the weight loss method of Example 1.
- Example 5 The procedure of Example 5 was repeated except that 50 g of ethyl lactate was used initially and a mixture of 0.30 g (0.85 equivalents) of DI water and 20.0 g of ethyl lactate was prepared and this mixture was fed to the reaction flask in a time period of ca. 8.0 minutes with stirring. After filtration, the solution was found to contain ca. 8.1% solids using the weight loss method of Example 1.
- Example 7 The procedure of Example 7 was repeated except that 50 g of propylene glycol monomethyl ether was used in place of the 2-methyl-1-butanol. After removing any insoluble materials by filtration through PFPE syringe filters, the solution was found to contain 2 to 3% solids using the weight loss method of Example 1.
- the film thickness was measured using an ellipsometer with refractive index input value of 1.77 (for alumina) before and after it was baked at 380° C. for 30 minutes under N 2 to determine the thermal stability of the film. Excellent thermal stability was observed for the cured films as evidenced by constant film thickness before and after baking at 380° C.
- Reaction mixture samples from Examples 5 and 6 were filtered through a 1.0 ⁇ m PFPE filter once to remove insoluble species in solutions.
- each of the two solutions was also filtered through a 0.2 ⁇ m PFPE filter 3 to 4 times before being processed.
- the process included spin coating the filtered solutions on a 200 mm bare silicon wafer at 1500 rpm followed by soft baking at 100° C. for 60 seconds. Film thicknesses were then measured using a THERMA-WAVE Spectroscopic Ellipsometer (Model 7341). The film thicknesses are reported in Table 2.
- the coated wafers were then cleaved into coupons of approximately 5 ⁇ 5 cm (2 ⁇ 2 inches), which were then subjected to curing bake at 400° C., for different curing times of 30, 60, 90 and 120 minutes in air.
- the test results exhibited a constant film thickness up to 90 minutes curing time. A slight film thickness drop was observed at 120 minutes curing time. The test results indicate that if a film is cured at 400° C. for 30 minutes the film thickness will remain unchanged for a subsequent 60 minute bake at the same temperature.
- a multilayer barrier structure having an aluminum oxide barrier layer and a silicon oxide barrier layer was prepared as follows.
- the reaction mixture from Example 5 was filtered through a 1.0 ⁇ m PFPE filter once and then through 0.2 ⁇ m PFPE filter multiple times before being processed.
- a silsesquioxane material was prepared as an oligomer of 50/9/15/26 tetraethyl orthosilicate/phenyl-trimethylsilane/vinyl-trimethylsilane/methyl-trimethylsilane in a 95/5 propylene glycol monomethylether acetate (PGMEA)/ethyl lactate solvent system using a known method.
- the formulation contained 2.18 wt % solids.
- the reaction mixture from Example 5 was spin coated at 1500 rpm followed by a curing bake at 350° C. for 60 seconds to form an aluminum oxide-containing film.
- a film of the silsesquioxane material was spin coated at 1500 rpm and then cured by baking at 350° C. for 60 seconds to form a silicon oxide-containing film.
- the total film thickness of the stack was then measured using the THERMA-WAVE Spectroscopic Ellipsometer as described in Example 11 and found to be 1902 ⁇ .
- Example 12 The procedure of Example 12 was repeated except that the reaction mixture from Example 6 was used as the organoaluminum compound coating composition. The total film thickness of the stack was then measured using the THERMA-WAVE Spectroscopic Ellipsometer as described in Example 11 and found to be 1950 ⁇ .
- Example 13 The procedure of Example 13 was repeated except that after the silisesquioxane film was cured, a second layer of the organoaluminum compound coating composition from Example 6 was spin coated on the surface of the cured silicon oxide-containing film and cured under the same conditions to form a second aluminum oxide-containing film. Next, a second layer of the silsesquioxane composition was spin coated on the surface of the second aluminum oxide-containing film, and then cured to form a second silicon oxide-containing film.
- This approach provided a multilayer (4-layer) barrier structure having alternating aluminum oxide-containing films and silicon oxide-containing films.
- the organoaluminum compound reaction mixture from Example 6 was spin coated at 1500 rpm followed by a curing bake at 350° C. for 2 minutes to form an aluminum oxide-containing film.
- a film of the polyphenylene resin available from The Dow Chemical Company under the trade name SiLK resins
- SiLK resins available from The Dow Chemical Company under the trade name SiLK resins
- PGMEA/cyclopentane/gamma-butyrolactone was spin coated at 1500 rpm followed by curing at 380° C. for 2 minutes.
- a second aluminum oxide-containing film was formed on the surface of the cured polyphenylene film by coating a layer of the composition from Example 6 on the surface of the cured polyphenylene film, and then aking at 380° C. for 30 minutes.
- a second polyphenylene layer was spin coated on the second aluminum oxide-containing film and cured under the same conditions as the first polyphenylene film.
- the resulting 4-layer stack had alternating layers of aluminum oxide-containing films and cured polyphenylene films.
- the organoaluminum compound coating composition from Example 6 was spin coated on a bare silicon wafer at 1500 rpm followed by curing at 400° C. for 30 minutes to form an aluminum oxide-containing film. On the cured aluminum oxide-containing film, another layer of the organoaluminum compound coating composition from Example 6 was spin coated and then cured under the same conditions. These coating and curing steps were performed two more times to provide a 4-layer aluminum oxide-containing barrier stack.
- Example 2 The ligand exchange procedure of Example 1 is repeated except that the ethyl lactate is replaced with diethyl tartrate.
- Example 2 The ligand exchange procedure of Example 1 is repeated except that the ethyl lactate is replaced with methyl glycolate.
- Example 2 The ligand exchange procedure of Example 1 is repeated except that the ethyl lactate is replaced with ethyl glycolate.
- Example 2 The ligand exchange procedure of Example 1 is repeated except that the ethyl lactate is replaced with 2-methyl-1-butanol.
- Example 2 The ligand exchange procedure of Example 1 is repeated except that the ethyl lactate is replaced with 4-methyl-2-pentanol.
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Abstract
Description
- The present invention relates generally to the field of solution-borne organometallic compounds, and more particularly to the field of manufacturing coated substrates using such solution-borne organometallic compounds.
- The need for certain layers having etch selectivity in lithography and layers for blocking both oxygen and moisture in certain semiconductor fabrications, such as organic light emitting diode (OLED) fabrications or photovoltaic devices, have lead to the use of films containing oxymetal domains in the manufacture of electronic devices. Oxymetal layers are generally characterized as films containing a majority of inorganic domains with (—M—O—)n linkages (oxymetal domains), where M is a metal and n>1, and may also be composed of minor amounts of other elements, such as carbon. Layers composed of mixed domains, such as containing both oxymetal domains and metal nitride domains, may be used.
- Conventional oxymetal films may contain one or more metals, such as Hf, Zr, Ti, W, Al, Ta and Mo, depending on the particular application. The etch resistance of oxymetal domain-containing films depends, in part, on the particular metal used as well as the level of (—M—O—)n domains present in the film, with an increased level of such domains providing greater etch resistance. Barrier films used in OLED applications conventionally contain Al or Si, that is (—Al—O—)n or (—Si—O—)n domains, respectively, where n>1. Aluminum oxide-containing films are known to have reduced transport of oxygen (O2), while silicon oxide-containing films are known to have reduced transport of moisture vapor. Any defects in such barrier films, such as pinholes, or any other defect causing incomplete coverage of the lower film presents a possible pathway for gas or vapor to access the lower film.
- Oxymetal films, such as alumina and silica films, are conventionally applied by chemical vapor deposition (CVD) onto an electronic device substrate. For example, International Pat. App. WO 2012/103390 discloses a stack having one or more oxide-containing barrier layers, such as aluminum oxide or silicon oxide layers, adjacent to a reactive inorganic layer on a flexible (plastic) substrate for reducing the transport of gas or vapor through the stack. According to this patent application, the reactive inorganic layer functions to react with any gas or vapor that penetrates through the barrier layer. This patent application fails to suggest any suitable materials for forming such barrier layers, and focuses on conventional film deposition techniques, such as vapor deposition techniques.
- Spin-on techniques are widely used in electronic device manufacture and offer advantages over conventional vapor deposition methods of depositing films. For example, spin-on techniques can use existing equipment, can be completed within a few minutes, and can provide a uniform coating over a substrate. Conventional aluminum sources, such as Al(Oi—Pr)3, suffer from very poor solubility in solvents conventionally used in electronic device manufacture as well as from high susceptibility to water/moisture. Such conventional aluminum sources typically form aluminum oxide particles upon exposure to moisture, such as the residual moisture found in common solvents. Such aluminum oxide particles pose problems in liquid dispensing systems and even if capable of being dispensed such particles pose defect issues during the manufacture of electronic devices. Accordingly, there is a need for aluminum sources and methods suitable for spin-on deposition of aluminum oxide-containing films for use as barriers in electronic device substrates. There is a further need for a method of depositing such aluminum oxide-containing barriers directly on an electronic device substrate rather than on a separate flexible (plastic) substrate.
- The present invention provides is a method of forming an aluminum oxide layer comprising: providing a substrate; disposing a layer of a coating composition on the substrate, wherein the coating composition comprises: an organoaluminum compound of the formula AlL1 xL2 y; wherein L1=(C1-C6)alkoxy; L2=(C5-C20)β-diketonate or OR1; R1=(C4-C10)hydrocarbyl moiety; x is an integer from 0 to 2; y is an integer from 1 to 3; and x+y=3; and (ii) an organic solvent having the formula HOR1; and curing the coating composition to form an aluminum oxide layer on the substrate.
- As used throughout this specification, the following abbreviations shall have the following meanings, unless the context clearly indicates otherwise: ca.=approximately; ° C.=degrees Celsius; g=grams; mmol=millimoles; mL=milliliters; μL=microliters; μm=micrometers=microns; nm=nanometers; Å=angstroms; and rpm=revolutions per minute. All amounts are percent by weight (“wt %”) and all ratios are molar ratios, unless otherwise noted. The term “oligomer” refers to dimers, trimers, tetramers and other relatively low molecular weight materials that are capable of further curing. “Alkyl” and “alkoxy” refer to linear, branched and cyclic alkyl and “alkoxy”, respectively. By the term “curing” is meant any process that polymerizes or otherwise increases, such as by condensation, the molecular weight of a film or layer. The articles “a”, “an” and “the” refer to the singular and the plural. All numerical ranges are inclusive and combinable in any order, except where it is clear that such numerical ranges are constrained to add up to 100%.
- Aluminum sources suitable for use in the present invention are those organoaluminum compounds of the formula AlL1 xL2 y; wherein L1=(C1-C6)alkoxy; L2=(C5-C20)β-diketonate or OR1; R1=(C4-C10)hydrocarbyl moiety; x is an integer from 0 to 2; y is an integer from 1 to 3; and x+y=3. Preferably, L1=(C1-C4)alkoxy, and more preferably (C1-C3)alkoxy. It is preferred that x is 0 or 1, and more preferably x=0. Preferably, L2=(C5-C15)β-diketonate or OR1, and more preferably L2=OR1. As used herein, “(C4-C10)hydrocarbyl” refers to any hydrocarbon moiety comprising 4-10 carbon atoms. Such (C4-C10)hydrocarbyl moiety may be aromatic or aliphatic, and preferably is aliphatic. The (C4-C10)hydrocarbyl moiety optionally comprises one or more substituents selected from the group consisting of hydroxyl, carboxylic acid and (C1-C6)alkyl carboxylate, preferably hydroxyl and (C1-C6)alkyl carboxylate, more preferably hydroxyl and (C1-C4)alkyl carboxylate, and yet more preferably hydroxyl and (C2-C4)alkyl carboxylate. It is further preferred that the (C4-C10)hydrocarbyl moiety of R1 be bound to the oxygen through a secondary carbon atom. It is preferred that y=2 or 3, and more preferably 3. Most preferred organoaluminum compounds are those of the formula AlL2 3, where L2 is as defined above. It will be appreciated by those skilled in the art that organoaluminum compounds useful as aluminum sources in the present invention may form dimers or trimers in solution, particularly if small amounts of water are present. Such dimers or trimers may be successfully used in the present method. Accordingly, in solution, the present organoaluminum compounds may have the formula AlmOm-1L1 x2L2 y2; wherein L1 and L2 are as defined above; m=an integer from 1 to 3; x2=0 to 4; y2=1 to 5; and x2+y2=m+2. Such dimers or trimers may be successfully used in the present method.
- The present organoaluminum compounds may be prepared by a variety of procedures known in the art, and are typically prepared by a ligand exchange reaction between a starting aluminum compound of the formula Al((C1-C6)alkoxy)3 and a suitable higher order ligand, such as HL2 or an alkali or alkaline earth salt thereof such as K+ −L2, where L2 is as defined above. Preferably, the higher order ligand used in the ligand exchange reaction has the formula HL2, and more preferably has the formula HOR1, where R1 is as defined above. In a general procedure, the starting aluminum compound Al((C1-C6)alkoxy)3 is combined with the higher order ligand and a suitable organic solvent in a flask. The mixture is then heated, typically to reflux, for a period of time to allow the desired ligand exchange to occur. Following this procedure, 1, 2 or all 3 of the (C1-C6)alkoxy ligands on the starting aluminum compound may be exchanged with a corresponding number of higher order ligands. It will be appreciated by those skilled in the art that the number of (C1-C6)alkoxy ligands replaced will depend on the steric hindrance of the particular (C1-C6)alkoxy ligand, the steric hindrance of the particular higher order ligand used, and the length of time the mixture is heated, with increasing length of time providing for greater ligand exchange. Suitable compounds useful as higher order ligands in the present invention include, but are not limited to: 2,4-octanedione; methyl glycolate; ethyl glycolate; ethyl lactate; 2-methyl-l-butanol; 4-methyl-2-pentanol; and diethyl tartrate. Preferred organic solvents are methyl glycolate; ethyl glycolate; ethyl lactate; and diethyl tartrate
- Any suitable organic solvent may be used for such ligand exchange reaction, and preferably the organic solvent has the formula HOR1, where R1 is as defined above. Preferably the higher order ligand is also used as the organic solvent for the ligand exchange reaction. In this way, a large excess of the higher order ligand is present, and typically all 3 of the (C1-C6)alkoxy ligands are replaced with higher order ligands, as indicated according to the following equation:
- When the organic solvent used for the ligand exchange reaction is not a solvent having the formula HOR1, then the organoaluminum compound comprising the higher order ligand, that is, Al(OR1)3 in the above equation, should be separated from such organic solvent and subsequently combined with a solvent having the formula HOR1.
- Preferred organic solvents for the ligand exchange reaction are those having the formula HOR1, where R1 is a (C4-C10)hydrocarbyl moiety, which is preferably aliphatic. Such (C4-C10)hydrocarbyl moiety may optionally comprise one or more substituents selected from the group consisting of hydroxyl, carboxylic acid and (C1-C6)alkyl carboxylate, preferably hydroxyl and (C1-C6)alkyl carboxylate, more preferably hydroxyl and (C1-C4)alkyl carboxylate, and yet more preferably hydroxyl and (C2-C4)alkyl carboxylate. Preferred organic solvents are α-hydroxy esters. It is also preferred that the (C4-C10)hydrocarbyl moiety of R1 be bound to the oxygen through a secondary carbon atom. Suitable organic solvents include, without limitation: methyl glycolate; ethyl glycolate; ethyl lactate; 2-methyl-1-butanol; 4-methyl-2-pentanol; and diethyl tartrate. Preferred organic solvents are methyl glycolate; ethyl glycolate; ethyl lactate; and diethyl tartrate.
- Coating compositions useful in the present method comprise an organoaluminum compound of the formula AlL1 xL2 y, as described above, and an organic solvent of the formula HOR1, also as described above. When the higher order ligand is also used as the organic solvent for the ligand exchange reaction, the reaction product may be used in the solvent without isolation. Preferably, the coating composition is filtered before use to remove any insoluble materials that form during the ligand exchange reaction.
- The present coating compositions may optionally include one or more surface leveling agents (or surfactants) or binder polymers. While any suitable surfactant may be used, such surfactants are typically non-ionic. The amount of such surfactants useful in the present compositions is well-known to those skilled in the art, and typically is in the range of 0 to 2% by weight. A wide variety of binder polymers may be used, such as to provide improved coating quality or leveling over the substrate. Suitable binder polymers are disclosed in U.S. patent application Ser. No. 13/776,496.
- Optionally, the present coating compositions may further comprise one or more curing agents to aid in the curing of the deposited organoaluminum film. Exemplary curing agents include thermal acid generators (TAGs) and photoacid generators (PAGs). Preferred curing agents are thermal acid generators. The amounts of such curing agents are within the ability of those skilled in the art. Any suitable curing agent may be used in the present coating compositions.
- The present coating compositions are useful in forming an aluminum oxide layer on various substrates, such as electronic device substrates, packaging substrates, separations substrates, or any other substrate where a gas barrier may be used. A wide variety of electronic device substrates may be used in the present invention, such as: packaging substrates such as multichip modules; flat panel display substrates, including flexible display substrates; integrated circuit substrates; photovoltaic device substrates; substrates for light emitting diodes (LEDs, including organic light emitting diodes or OLEDs); semiconductor wafers; polycrystalline silicon substrates; and the like. Such substrates are typically composed of one or more of silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates may be in the form of wafers such as those used in the manufacture of integrated circuits, optical sensors, flat panel displays, integrated optical circuits, and LEDs. As used herein, the term “semiconductor wafer” is intended to encompass “an electronic device substrate,” “a semiconductor substrate,” “a semiconductor device,” and various packages for various levels of interconnection, including a single-chip wafer, multiple-chip wafer, packages for various levels, or other assemblies requiring solder connections. Particularly suitable substrates for hardmask layers are patterned wafers, such as patterned silicon wafers, patterned sapphire wafers, and patterned gallium-arsenide wafers. Such wafers may be any suitable size. Preferred wafer diameters are 200 mm to 300 mm, although wafers having smaller and larger diameters may be suitably employed according to the present invention. As used herein, the term “semiconductive substrates” includes any substrate having one or more semiconductor layers or structures which include active or operable portions of semiconductor devices. The term “semiconductor substrate” is defined to mean any construction comprising semiconductive material, including but not limited to bulk semiconductive material such as a semiconductive wafer, either alone or in assemblies comprising other materials thereon, and semiconductive material layers, either alone or in assemblies comprising other materials. A semiconductor device refers to a semiconductor substrate upon which at least one microelectronic device has been or is being batch fabricated. Preferred substrates are substrates for LEDs, and more preferably for OLEDs. Also preferred are flexible display substrates and photovoltaic device substrates, and more preferred are flexible display substrates for LEDs, and more preferably for OLEDs.
- A layer of the present coating compositions may be disposed on a substrate, such as an electronic device substrate, by any suitable means, such as spin-coating, spray coating, slot-die coating, doctor blading, curtain coating, roller coating, dip coating, and the like. Spin-coating, spray coating and slot-die coating are preferred. In a typical spin-coating method, the present coating compositions are applied to an electronic device substrate which is spinning at a rate of 500 to 4000 rpm for a period of 15-90 seconds to obtain a desired layer of the organoaluminum compound on the substrate. It will be appreciated by those skilled in the art that the height of the organoaluminum compound layer may be adjusted by changing the spin speed, as well as the percentage solids in the coating composition.
- During or after the deposition of a layer of the present coating compositions on a substrate, the layer is optionally baked at a relatively low temperature to remove any remaining solvent and other relatively volatile components to form a layer of the organoaluminum compound. Typically, the substrate is baked at a temperature of ≦125° C., preferably from 60 to 125° C., and more preferably from 90 to 115° C. The baking time is typically from 10 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, and more preferably from 6 to 180 seconds. When the substrate is a wafer, such baking step may be performed by heating the wafer on a hot plate.
- Following any baking step to remove solvent, the organoaluminum compound layer is cured, such as in an oxygen-containing atmosphere, such as air. The curing step is conducted preferably on a hot plate-style apparatus, though oven curing may be used to obtain equivalent results. Typically, such curing is performed by heating the organoaluminum compound layer at a curing temperature of ≧150° C., preferably 150 to 450° C., and more preferably from 200 to 400° C. The choice of final curing temperature depends mainly upon the desired curing rate, with higher curing temperatures requiring shorter curing times. Typically, the curing time may be from 10 seconds to 120 minutes. Shorter curing times are preferred, and are typically from 10 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, and more preferably from 30 seconds to 3 minutes. It will be appreciated by those skilled in the art that longer curing times may be used. This curing step is performed in order to thermally decompose at least a portion of the organoaluminum compound, and preferably all of the organoaluminum compound, so that a hardmask layer containing oxyaluminum domains (aluminum oxide) having an (—M—O—)n linkage, where n>1, preferably n>2, more preferably n>5, yet more preferably n>10, and even more preferably n>25 are obtained. Typically, the amount of aluminum in the cured oxyaluminum domain-containing films may be up to 95 mol % (or even higher), and preferably from 50 to 95 mol %. Aluminum oxide layers formed from the present compositions contain oxy-aluminum domains, and may contain other domains, such as aluminum nitride domains, as well as optionally containing carbon, such as an amount of up to 5 mol % carbon.
- When the present composition comprises an optional TAG, the organoaluminum compound layer should be heated to a temperature sufficient to activate the TAG and generate an acid. Typically, the temperature used to cure the organoaluminum compound layer to form the aluminum oxide-containing layer is sufficient to activate the TAG. Alternatively, when a PAG is used in the present compositions, the organoaluminum compound layer may be exposed to light of an appropriate wavelength or to an electron beam to generate the corresponding acid. Such exposure step may occur before, during or both before and during the step of curing the organoaluminum compound layer to form the aluminum oxide-containing film.
- When the present organoaluminum layers are cured at temperatures ≧200° C., the resulting aluminum oxide-containing films are resistant to stripping (being removed) by solvents conventionally used in the application of antireflective coatings and photoresists. When the present organoaluminum oligomer layers are cured at temperatures ≧350° C., the resulting aluminum oxide-containing films are also resistant to stripping by alkaline or solvent developers conventionally used in the development of imaged photoresist layers.
- The initial baking step may not be necessary if the final curing step is conducted in such a way that rapid evolution of the solvents and curing by-products is not allowed to disrupt the film quality. For example, a ramped bake beginning at relatively low temperatures and then gradually increasing to the range of 250 to 400° C. can give acceptable results. It can be preferable in some cases to have a two-stage curing process, with the first stage being a lower bake temperature of less than 250° C., and the second stage being a higher bake temperature preferably between 250 and 400° C. Two stage curing processes facilitate uniform filling and planarization of pre-existing substrate surface topography.
- While not wishing to be bound by theory, it is believed that the conversion of the organoaluminum to aluminum oxide involves hydrolysis by moisture that is contained in the coating and/or adsorbed from the atmosphere during the deposition (casting) and curing processes. Therefore, the curing process is preferably carried out in air or in an atmosphere where moisture is present to facilitate complete conversion to aluminum oxide. The curing process can also be aided by exposure of the coating to ultraviolet radiation, preferably in a wavelength range of from about 200 to 400 nm The exposure process can be applied separately or in conjunction with a thermal curing process.
- The cured aluminum oxide-containing layer (or film) may suitably be used as a hardmask, dielectric layer, barrier layer or for any other suitable use in the manufacture of various devices. The cured aluminum oxide-containing layers of the present invention are particularly suitable for use as a barrier layer, such as an oxygen barrier, in the manufacture of LEDs, and preferably in the manufacture of OLEDs, or in packaging applications or as a low diffusion gas barrier in separations applications.
- Depending on the particular application, the present aluminum oxide-containing layers may be subjected to further processing steps, such as patterning. Such further processing steps may require the application of one or more organic materials, such as photoresists and antireflective coatings, to the surface of the aluminum oxide-containing layer. Oxy-metal containing layers typically have a surface energy that is very different from that of subsequently applied organic layers. Such a mismatch of surface energy causes poor adhesion between the oxymetal hardmask layer and the subsequently applied organic layer. In the case of a subsequently applied photoresist layer, such mismatch in surface energy results in severe pattern collapse. In order to make the surface of the present aluminum oxide-containing films more compatible with subsequently applied organic layers, the surface may optionally be treated with an appropriate surface treating agent.
- Surface treating compositions useful for treating the present aluminum oxide-containing films surface are those disclosed in U.S. patent application Ser. No. 13/745,752 and comprise an organic solvent and a surface treating agent, where the surface treating agent comprises one or more surface treating moieties. Optionally, the surface treating composition may further comprise one or more additives, such as thermal acid generators, photoacid generators, antioxidants, dyes, contrast agents, and the like. A wide variety of organic solvents may suitably be used, such as, but are not limited to, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, lactones, esters, glycols, glycol ethers, and mixtures thereof. Exemplary organic solvents include, without limitation, toluene, xylene, mesitylene, alkylnaphthalenes, 2-methyl-1-butanol, 4-methyl-2-pentanol, gamma-butyrolactone, ethyl lactate, 2-hydroxyisobutyric acid methyl ester, propylene glycol methyl ether acetate, and propylene glycol methyl ether. Suitable solvents have a relatively higher vapor pressure than the surface treating agent, such that the solvent may be removed from the surface of the film leaving behind the surface treating agent. It is preferred that the organic solvents do not have free carboxylic acid groups or sulfonic acid groups. A wide variety of surface treating agents may be used in the surface treating compositions and may be polymeric or non-polymeric, and comprise one or more surface treating moieties. Exemplary surface treating moieties include hydroxyl (—OH), thiol (—SH), carboxyl (—CO2H), betadiketo (—C(O)—CH2—C(O)—), protected carboxyl, and protected hydroxyl groups. While amino groups will work, it is preferred that the surface treating agents are free of amino groups, and preferably free of nitrogen, as such groups may adversely affect the function of subsequently applied coatings such as chemically amplified photoresists. Protected carboxyl groups and protected hydroxyl groups are any groups which are cleavable under certain conditions to yield a carboxyl group or hydroxyl group, respectively. Such protected carboxyl groups and protected hydroxyl groups are well-known in the art. When the surface treating agent comprises one or more protected hydroxyl groups, it is preferred that a TAG or PAG be used in the surface treating composition.
- Alternatively, rather than separately treating the formed aluminum oxide-containing layer with a surface treating agent, the present organoaluminum compound coating compositions may further comprise a surface treating agent having a surface energy of 20 to 40 erg/cm2 and comprising a surface treating moiety chosen from hydroxyl, protected hydroxyl, protected carboxyl, and mixtures thereof, such as those described in copending U.S. patent application Ser. No. 13/745,753. A minimum of one surface treating moiety per surface treating agent molecule is required. There is no specific limit to the number of surface treating moieties per surface treatment agent molecule, as long as the surface energy of the surface treating agent has a (static) surface energy in the range of 20 to 40 erg/cm2. It will be appreciated by those skilled in the art that increasing the amount of surface treating moieties in the surface treating agent molecule typically increases the surface energy of the molecule. When added to the organoaluminum coating compositions, the surface treating agent is substantially free of un-protected carboxylic acid groups (that is, the surface treating agent comprises ≦0.5 mol % un-protected or “free” carboxylic acid groups). In addition to the surface treating moiety, the surface treating agent also comprises one or more relatively more hydrophobic moieties, such as C3-20alkyl groups and C6-20aryl groups. It is believed that a branched or cyclic alkyl group is relatively more hydrophobic than the corresponding linear alkyl group, and that increasing the branching or cyclic nature of such a group helps lower the surface energy of the surface treating agent. Likewise, alkyl and aryl groups of increasing carbon chain length also lower the surface energy of the surface treating agent. When such a surface treating agent is added to the present organoaluminum coating compositions, a solvent system comprising a majority of a first solvent having a relatively low surface energy and a minority of a second solvent having a relatively higher boiling point than the first solvent, and where the second solvent has a higher surface energy (tension) than the surface energy of the surface treating agent.
- While not wishing to be bound by theory, it is believed that when the surface treating agent is present in the organoaluminum coating compositions, the surface treating agent migrates toward the surface of the forming film during deposition of the coating compositions and/or during any subsequent solvent removal step. It is further believed that the relatively lower surface energy of the surface treating agent helps drive the surface treating agent to the air interface. It will be appreciated by those skilled in the art that such migration of the surface treating agent should substantially occur before the complete curing of the aluminum oxide-containing film. The formation of a cured aluminum oxide-containing film substantially prohibits migration of the surface treating agent. As the surface treating agent is present at the surface of the organoaluminum compound layer, the temperature used to cure the organoaluminum compound layer should be selected such that the surface treating agent does not substantially decompose. If higher curing temperatures are required, then more thermally stable surface treating agents, such as vinylaryl polymers such as hydroxystyrene polymers and polyhedral oligosilsesquioxane polymers may be used.
- As surface energy is often difficult to measure, surrogate measurements, such as water contact angles, are typically used. The determination of water contact angles is well-known, and a preferred method uses using a Kruss drop shape analyzer Model 100, using deionized (“DI”) water and a 2.5 μL drop size. Oxy-metal containing layers, such as aluminum oxide-containing layers, typically have a water contact angle of ≦50°, such as from 35 to 45°. Following treatment with a surface treating composition, the aluminum oxide-containing film surface typically has a water contact angle of ≧55°, such as from 55 to 70°. Following treatment with the surface treating agent, the aluminum oxide-containing film surface has a surface energy that substantially matches that of a subsequently applied organic layer, that is, the surface energy of the treated aluminum oxide-containing layer should be within 20% of the surface energy of a subsequently applied organic layer. Subsequent processing steps involving organic layers applied over the aluminum oxide-containing layer will have fewer defects as compared to aluminum oxide-containing films without such surface treatment.
- 4.0 g of aluminum tri-isopropoxide (Al(Oi—Pr)3) was mixed with 50.0 g of ethyl lactate in a 250 mL round bottom flask fitted with a heating mantle and connected to a condenser. The ethyl lactate was not anhydrous and therefore contained a residual amount of water. With adequate stirring (magnetic stirring bar), the mixture was heated was heated to 88° C. (controlled by through a thermocouple) and maintained at this temperature for 2 hours. It was then brought to reflux and held at reflux for 1.5 hours. Heating was then stopped and the mixture was allowed to cool naturally to room temperature with stirring. Next, the solution was filtered through a 1.0 um perfluoropolyethylene (PFPE) syringe filter to remove any insoluble materials, and then filtered through a 0.2 μm PFPE filter. The filtered solution was found to contain ca. 13.2% solid using the following weight loss method. This ligand exchange reaction in excess ethyl lactate provided tris((1-ethoxy-1-oxopropan-2-yl)oxy)aluminum.
- Weight Loss Method: Approximately 0.1 g of an obtained organoaluminum compound in solution was weighed into a tared aluminum pan. Approximately 0.5 g of the solvent used to form the organoaluminum compound (ethyl lactate) was added to the aluminum pan to dilute the test solution to make it cover the aluminum pan more evenly. The aluminum pan was heated in a thermal oven at approximately 110° C. for 15 minutes. After the aluminum pan cooled to room temperature, the weight of the aluminum pan with dried solid film was determined, and the percentage solid content was calculated.
- 4.0 g of Al(Oi—Pr)3 was mixed with 50.0 g of ethyl lactate and 0.1 g (0.28 equivalents) of deionized (DI) water in a 250 mL round bottom flask fitted with a heating mantle and connected to a condenser. The ethyl lactate was not anhydrous and therefore contained a residual amount of water. With adequate stirring (magnetic stirring bar), the mixture was heated to 88° C. (controlled by through a thermocouple) and maintained at this temperature for 2 hours. It was then brought to reflux temperature and held at reflux for 1.5 hours. Heating was then stopped and the mixture was allowed to cool naturally to room temperature with stirring. The solution was then filtered through a 1.0 μm PFPE filter to remove any insoluble materials, and then filtered through a 0.2 μm PFPE filter. The filtered solution was found to contain ca. 8.8% solids using the weight loss method described in Example 1.
- Example 2 was repeated except that 0.2 g (0.57 equivalents) of DI water was used. After filtering, the solution was found to contain ca. 7.8% solids using the weight loss method described in Example 1.
- The procedure of Example 2 was repeated except that 0.5 g (1.42 equivalents) of DI water was used. After filtration, the solution was found to contain ca. 6.7% solids using the weight loss method of Example 1.
- 4.0 g of Al(Oi—Pr)3 was mixed with 55.2 g of ethyl lactate in a 250 mL round bottom flask fitted with a heating mantle and connected to a condenser. The ethyl lactate was not anhydrous. With adequate stirring by way of magnetic stirring bar, the mixture was heated to reflux temperature and maintained at reflux for 2 hours. Heating was then stopped and the mixture was allowed to cool naturally to room temperature with stirring. Next 0.20 g (0.57 equivalents) of DI water and 15.0 g of ethyl lactate was mixed and the mixture was fed to the reaction flask over ca. 6.5 minutes with stirring. The reaction mixture was then heated to reflux temperature again and held at reflux for 2 hours, after which heating was stopped and the reaction mixture was allowed to cool naturally to room temperature. The reaction mixture solution was then filtered through a 1.0 μm PFPE filter to remove any insoluble materials, and then filtered through a 0.2 μm PFPE filter. After filtration, the solution was found to contain ca. 7.9% solids using the weight loss method of Example 1.
- The procedure of Example 5 was repeated except that 50 g of ethyl lactate was used initially and a mixture of 0.30 g (0.85 equivalents) of DI water and 20.0 g of ethyl lactate was prepared and this mixture was fed to the reaction flask in a time period of ca. 8.0 minutes with stirring. After filtration, the solution was found to contain ca. 8.1% solids using the weight loss method of Example 1.
- 4.0 g of Al(Oi—Pr)3 was added to 50 g of 2-methyl-1-butanol in a round bottom flask equipped with a heating mantle and a condenser. The mixture was then heated to the reflux temperature and held at the temperature for 5 hours. After removing any insoluble materials by filtration through PFPE syringe filters, the solution was found to contain 2 to 3% solids using the weight loss method of Example 1.
- The procedure of Example 7 was repeated except that 50 g of propylene glycol monomethyl ether was used in place of the 2-methyl-1-butanol. After removing any insoluble materials by filtration through PFPE syringe filters, the solution was found to contain 2 to 3% solids using the weight loss method of Example 1.
- 6.5 g of the reaction mixture from Example 1 was weighed into a 20 mL glass vial along with 6.5 g of ethyl lactate. This diluted solution was then filtered through a 1.0 μm PFPE syringe filter once and then filtered through a 0.2 μm PFPE syringe filter multiple times into another 20 mL glass vial. The filtered sample was coated on different 200 mm (8 inch) silicon wafers at 1500 rpm. One wafer was then cured at each of 200, 250 and 350° C. for 60 seconds. The film thickness of the cured films was measured using a Therma-wave spectroscopic ellipsometer (Model 7341) 673 nm wavelength, and is summarized in Table 1.
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TABLE 1 Curing Temperature, ° C. Film Thickness, Å 200 1324 250 1165 350 834 - Visual inspection of the wafers showed that all the films were of good quality. Each of the cured films was washed with ethyl lactate for 10 seconds, and no film stripping was observed, indicating the formation of a crosslinked network.
- 7.5 lg of the reaction mixture from Example 3 was weighed into a 20 mL glass vial and mixed with 7.69 g of ethyl lactate. This diluted solution was then filtered through a 1.0 μm PFPE syringe filter once and then filtered through a 0.2 μm PFPE syringe filter multiple times into another 20 mL glass vial. The filtered sample was coated on a 200 mm (8 inch) bare silicon wafer at 1500 rpm followed by baking the coated film at 100° C. for 60 seconds. The coated wafer was then cured in a furnace at 400° C. for 30 minutes under air. Visually, the cured film was silver (aluminum like) in color and of a nicely formed film quality. The film thickness was measured using an ellipsometer with refractive index input value of 1.77 (for alumina) before and after it was baked at 380° C. for 30 minutes under N2 to determine the thermal stability of the film. Excellent thermal stability was observed for the cured films as evidenced by constant film thickness before and after baking at 380° C.
- Reaction mixture samples from Examples 5 and 6 were filtered through a 1.0 μm PFPE filter once to remove insoluble species in solutions. For this curing test, each of the two solutions was also filtered through a 0.2 μm PFPE filter 3 to 4 times before being processed. The process included spin coating the filtered solutions on a 200 mm bare silicon wafer at 1500 rpm followed by soft baking at 100° C. for 60 seconds. Film thicknesses were then measured using a THERMA-WAVE Spectroscopic Ellipsometer (Model 7341). The film thicknesses are reported in Table 2.
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TABLE 2 Sample Film Thickness, Å Example 5 2320 Example 6 2496 - Visually, very nice quality of films were obtained without noticable defectivity or haze. The coated wafers were then cleaved into coupons of approximately 5×5 cm (2×2 inches), which were then subjected to curing bake at 400° C., for different curing times of 30, 60, 90 and 120 minutes in air. The test results exhibited a constant film thickness up to 90 minutes curing time. A slight film thickness drop was observed at 120 minutes curing time. The test results indicate that if a film is cured at 400° C. for 30 minutes the film thickness will remain unchanged for a subsequent 60 minute bake at the same temperature.
- A multilayer barrier structure having an aluminum oxide barrier layer and a silicon oxide barrier layer was prepared as follows. The reaction mixture from Example 5 was filtered through a 1.0 μm PFPE filter once and then through 0.2 μm PFPE filter multiple times before being processed.
- A silsesquioxane material was prepared as an oligomer of 50/9/15/26 tetraethyl orthosilicate/phenyl-trimethylsilane/vinyl-trimethylsilane/methyl-trimethylsilane in a 95/5 propylene glycol monomethylether acetate (PGMEA)/ethyl lactate solvent system using a known method. The formulation contained 2.18 wt % solids.
- On a silicon wafer, the reaction mixture from Example 5 was spin coated at 1500 rpm followed by a curing bake at 350° C. for 60 seconds to form an aluminum oxide-containing film. On the cured aluminum oxide-containing film, a film of the silsesquioxane material was spin coated at 1500 rpm and then cured by baking at 350° C. for 60 seconds to form a silicon oxide-containing film. The total film thickness of the stack was then measured using the THERMA-WAVE Spectroscopic Ellipsometer as described in Example 11 and found to be 1902 Å.
- The procedure of Example 12 was repeated except that the reaction mixture from Example 6 was used as the organoaluminum compound coating composition. The total film thickness of the stack was then measured using the THERMA-WAVE Spectroscopic Ellipsometer as described in Example 11 and found to be 1950 Å.
- The procedure of Example 13 was repeated except that after the silisesquioxane film was cured, a second layer of the organoaluminum compound coating composition from Example 6 was spin coated on the surface of the cured silicon oxide-containing film and cured under the same conditions to form a second aluminum oxide-containing film. Next, a second layer of the silsesquioxane composition was spin coated on the surface of the second aluminum oxide-containing film, and then cured to form a second silicon oxide-containing film. This approach provided a multilayer (4-layer) barrier structure having alternating aluminum oxide-containing films and silicon oxide-containing films.
- On a silicon wafer, the organoaluminum compound reaction mixture from Example 6 was spin coated at 1500 rpm followed by a curing bake at 350° C. for 2 minutes to form an aluminum oxide-containing film. On the cured aluminum oxide-containing film, a film of the polyphenylene resin (available from The Dow Chemical Company under the trade name SiLK resins) as a 10.8 wt % solution in 88.2/9.8/2 PGMEA/cyclopentane/gamma-butyrolactone was spin coated at 1500 rpm followed by curing at 380° C. for 2 minutes. Next, a second aluminum oxide-containing film was formed on the surface of the cured polyphenylene film by coating a layer of the composition from Example 6 on the surface of the cured polyphenylene film, and then aking at 380° C. for 30 minutes. A second polyphenylene layer was spin coated on the second aluminum oxide-containing film and cured under the same conditions as the first polyphenylene film. The resulting 4-layer stack had alternating layers of aluminum oxide-containing films and cured polyphenylene films.
- The organoaluminum compound coating composition from Example 6 was spin coated on a bare silicon wafer at 1500 rpm followed by curing at 400° C. for 30 minutes to form an aluminum oxide-containing film. On the cured aluminum oxide-containing film, another layer of the organoaluminum compound coating composition from Example 6 was spin coated and then cured under the same conditions. These coating and curing steps were performed two more times to provide a 4-layer aluminum oxide-containing barrier stack.
- The ligand exchange procedure of Example 1 is repeated except that the ethyl lactate is replaced with diethyl tartrate.
- The ligand exchange procedure of Example 1 is repeated except that the ethyl lactate is replaced with methyl glycolate.
- The ligand exchange procedure of Example 1 is repeated except that the ethyl lactate is replaced with ethyl glycolate.
- The ligand exchange procedure of Example 1 is repeated except that the ethyl lactate is replaced with 2-methyl-1-butanol.
- The ligand exchange procedure of Example 1 is repeated except that the ethyl lactate is replaced with 4-methyl-2-pentanol.
Claims (11)
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20160133689A1 (en) * | 2014-11-06 | 2016-05-12 | Texas Instruments Incorporated | Reliability improvement of polymer-based capacitors by moisture barrier |
US9515272B2 (en) | 2014-11-12 | 2016-12-06 | Rohm And Haas Electronic Materials Llc | Display device manufacture using a sacrificial layer interposed between a carrier and a display device substrate |
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US9136123B2 (en) | 2013-01-19 | 2015-09-15 | Rohm And Haas Electronic Materials Llc | Hardmask surface treatment |
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US9296879B2 (en) | 2013-09-03 | 2016-03-29 | Rohm And Haas Electronic Materials Llc | Hardmask |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6258157B1 (en) * | 1997-04-17 | 2001-07-10 | President And Fellows Of Harvard College | Liquid precursors for formation of metal oxides |
US6495709B1 (en) * | 2000-03-16 | 2002-12-17 | Symetrix Corporation | Liquid precursors for aluminum oxide and method making same |
US20030176065A1 (en) * | 2002-03-14 | 2003-09-18 | Vaartstra Brian A. | Aluminum-containing material and atomic layer deposition methods |
US20040071879A1 (en) * | 2000-09-29 | 2004-04-15 | International Business Machines Corporation | Method of film deposition, and fabrication of structures |
US20050003662A1 (en) * | 2003-06-05 | 2005-01-06 | Jursich Gregory M. | Methods for forming aluminum containing films utilizing amino aluminum precursors |
US7615250B2 (en) * | 2005-02-14 | 2009-11-10 | Praxair Technology, Inc. | Organoaluminum precursor compounds |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2881847B2 (en) | 1988-12-15 | 1999-04-12 | 日産化学工業株式会社 | Coating composition and method for producing the same |
US5510147A (en) | 1995-03-03 | 1996-04-23 | International Paper Company | Sol gel barrier films |
US6380105B1 (en) | 1996-11-14 | 2002-04-30 | Texas Instruments Incorporated | Low volatility solvent-based method for forming thin film nanoporous aerogels on semiconductor substrates |
KR100510281B1 (en) | 2000-07-25 | 2005-08-30 | 간사이 페인트 가부시키가이샤 | Coating material for forming titanium oxide film, method for forming titanium oxide film and use of said coating material |
BR112013019014A2 (en) | 2011-01-27 | 2016-10-04 | Vitriflex Inc | stack of inorganic multilayers and methods and compositions related to this |
US9070548B2 (en) | 2012-03-06 | 2015-06-30 | Rohm And Haas Electronic Materials Llc | Metal hardmask compositions |
-
2013
- 2013-07-22 US US13/947,129 patent/US8927439B1/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6258157B1 (en) * | 1997-04-17 | 2001-07-10 | President And Fellows Of Harvard College | Liquid precursors for formation of metal oxides |
US6495709B1 (en) * | 2000-03-16 | 2002-12-17 | Symetrix Corporation | Liquid precursors for aluminum oxide and method making same |
US20040071879A1 (en) * | 2000-09-29 | 2004-04-15 | International Business Machines Corporation | Method of film deposition, and fabrication of structures |
US20030176065A1 (en) * | 2002-03-14 | 2003-09-18 | Vaartstra Brian A. | Aluminum-containing material and atomic layer deposition methods |
US20050003662A1 (en) * | 2003-06-05 | 2005-01-06 | Jursich Gregory M. | Methods for forming aluminum containing films utilizing amino aluminum precursors |
US7615250B2 (en) * | 2005-02-14 | 2009-11-10 | Praxair Technology, Inc. | Organoaluminum precursor compounds |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20160133689A1 (en) * | 2014-11-06 | 2016-05-12 | Texas Instruments Incorporated | Reliability improvement of polymer-based capacitors by moisture barrier |
US9793106B2 (en) * | 2014-11-06 | 2017-10-17 | Texas Instruments Incorporated | Reliability improvement of polymer-based capacitors by moisture barrier |
US9515272B2 (en) | 2014-11-12 | 2016-12-06 | Rohm And Haas Electronic Materials Llc | Display device manufacture using a sacrificial layer interposed between a carrier and a display device substrate |
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