WO2009099325A1 - Method for manufacturing a multi_layer stack structure with improved wvtr barrier property - Google Patents
Method for manufacturing a multi_layer stack structure with improved wvtr barrier property Download PDFInfo
- Publication number
- WO2009099325A1 WO2009099325A1 PCT/NL2009/050027 NL2009050027W WO2009099325A1 WO 2009099325 A1 WO2009099325 A1 WO 2009099325A1 NL 2009050027 W NL2009050027 W NL 2009050027W WO 2009099325 A1 WO2009099325 A1 WO 2009099325A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- treatment space
- layer
- substrates
- plasma
- electrodes
- Prior art date
Links
- 230000004888 barrier function Effects 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000010410 layer Substances 0.000 claims abstract description 85
- 239000000758 substrate Substances 0.000 claims abstract description 83
- 238000010030 laminating Methods 0.000 claims abstract description 16
- 239000012790 adhesive layer Substances 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000002243 precursor Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 238000000151 deposition Methods 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000004891 communication Methods 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 239000011147 inorganic material Substances 0.000 claims description 2
- 210000002381 plasma Anatomy 0.000 description 48
- 239000010408 film Substances 0.000 description 32
- 239000000428 dust Substances 0.000 description 31
- 230000015572 biosynthetic process Effects 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 15
- 230000008021 deposition Effects 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 14
- 239000000853 adhesive Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 12
- 239000011575 calcium Substances 0.000 description 11
- 230000015271 coagulation Effects 0.000 description 11
- 238000005345 coagulation Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000004973 liquid crystal related substance Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 230000007547 defect Effects 0.000 description 7
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 7
- -1 PolyEthylene Polymers 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 238000003475 lamination Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910052756 noble gas Inorganic materials 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000009832 plasma treatment Methods 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 2
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- WHYHZFHCWGGCOP-UHFFFAOYSA-N germyl Chemical compound [GeH3] WHYHZFHCWGGCOP-UHFFFAOYSA-N 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- VNNDVNZCGCCIPA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;manganese Chemical compound [Mn].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VNNDVNZCGCCIPA-FDGPNNRMSA-N 0.000 description 1
- ANZPUCVQARFCDW-UHFFFAOYSA-N 2,2,4,4,6,6-hexamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C[Si]1(C)O[SiH2]O[Si](C)(C)O[Si](C)(C)O1 ANZPUCVQARFCDW-UHFFFAOYSA-N 0.000 description 1
- NGCRLFIYVFOUMZ-UHFFFAOYSA-N 2,3-dichloroquinoxaline-6-carbonyl chloride Chemical compound N1=C(Cl)C(Cl)=NC2=CC(C(=O)Cl)=CC=C21 NGCRLFIYVFOUMZ-UHFFFAOYSA-N 0.000 description 1
- ONTKLXRYXKPSIE-UHFFFAOYSA-M CCCOC(CC(=O)O[Ti])OCCC Chemical compound CCCOC(CC(=O)O[Ti])OCCC ONTKLXRYXKPSIE-UHFFFAOYSA-M 0.000 description 1
- ATJDCQWLPDJCAA-UHFFFAOYSA-N CCO[Ti](CC)(OCC)OCC Chemical compound CCO[Ti](CC)(OCC)OCC ATJDCQWLPDJCAA-UHFFFAOYSA-N 0.000 description 1
- XUDHTERFOUHVEQ-UHFFFAOYSA-N CC[Ti] Chemical compound CC[Ti] XUDHTERFOUHVEQ-UHFFFAOYSA-N 0.000 description 1
- FWMGWNBHJYBRTH-UHFFFAOYSA-N CC[Ti](CC)(CC)CC Chemical compound CC[Ti](CC)(CC)CC FWMGWNBHJYBRTH-UHFFFAOYSA-N 0.000 description 1
- NZJAPVDYYDAION-UHFFFAOYSA-N CC[Ti](CC)CC Chemical compound CC[Ti](CC)CC NZJAPVDYYDAION-UHFFFAOYSA-N 0.000 description 1
- UXONDUQQZFSKGP-UHFFFAOYSA-N CO[Ti](C)OC Chemical compound CO[Ti](C)OC UXONDUQQZFSKGP-UHFFFAOYSA-N 0.000 description 1
- IBPZLIKXZXLHIE-UHFFFAOYSA-N C[Ti+3].CCC[O-].CCC[O-].CCC[O-] Chemical compound C[Ti+3].CCC[O-].CCC[O-].CCC[O-] IBPZLIKXZXLHIE-UHFFFAOYSA-N 0.000 description 1
- QDGMSMUNXGCWRA-UHFFFAOYSA-N C[Ti](C)N Chemical compound C[Ti](C)N QDGMSMUNXGCWRA-UHFFFAOYSA-N 0.000 description 1
- COOXAWDWHWRVRD-UHFFFAOYSA-N C[Ti]C Chemical compound C[Ti]C COOXAWDWHWRVRD-UHFFFAOYSA-N 0.000 description 1
- 229910021012 Co2(CO)8 Inorganic materials 0.000 description 1
- 229910019813 Cr(CO)6 Inorganic materials 0.000 description 1
- JOOMLFKONHCLCJ-UHFFFAOYSA-N N-(trimethylsilyl)diethylamine Chemical compound CCN(CC)[Si](C)(C)C JOOMLFKONHCLCJ-UHFFFAOYSA-N 0.000 description 1
- YKFRUJSEPGHZFJ-UHFFFAOYSA-N N-trimethylsilylimidazole Chemical compound C[Si](C)(C)N1C=CN=C1 YKFRUJSEPGHZFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910010066 TiC14 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 229910008940 W(CO)6 Inorganic materials 0.000 description 1
- 229910009035 WF6 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 description 1
- YTEISYFNYGDBRV-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)oxy-dimethylsilyl]oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)(C)O[Si](C)C YTEISYFNYGDBRV-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- WYUIWUCVZCRTRH-UHFFFAOYSA-N [[[ethenyl(dimethyl)silyl]amino]-dimethylsilyl]ethene Chemical compound C=C[Si](C)(C)N[Si](C)(C)C=C WYUIWUCVZCRTRH-UHFFFAOYSA-N 0.000 description 1
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 description 1
- SBRQYVYPHCFSDQ-UHFFFAOYSA-L [acetyloxy(ditert-butyl)stannyl] acetate Chemical compound CC(=O)O[Sn](C(C)(C)C)(C(C)(C)C)OC(C)=O SBRQYVYPHCFSDQ-UHFFFAOYSA-L 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RQTQBQMVIJMUPB-UHFFFAOYSA-N butan-1-ol titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO RQTQBQMVIJMUPB-UHFFFAOYSA-N 0.000 description 1
- MXTOFRMIIQQSOE-UHFFFAOYSA-N butane;titanium(4+) Chemical compound [Ti+4].CCC[CH2-].CCC[CH2-].CCC[CH2-].CCC[CH2-] MXTOFRMIIQQSOE-UHFFFAOYSA-N 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- WOXHFVAKSNVTGB-UHFFFAOYSA-N butyl-dimethyl-(3-piperazin-1-ylpropyl)silane Chemical compound CCCC[Si](C)(C)CCCN1CCNCC1 WOXHFVAKSNVTGB-UHFFFAOYSA-N 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- LVGLLYVYRZMJIN-UHFFFAOYSA-N carbon monoxide;rhodium Chemical compound [Rh].[Rh].[Rh].[Rh].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] LVGLLYVYRZMJIN-UHFFFAOYSA-N 0.000 description 1
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical compound [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- SXSNZRHGAMVNJE-UHFFFAOYSA-N chloro-[[[chloromethyl(dimethyl)silyl]amino]-dimethylsilyl]methane Chemical compound ClC[Si](C)(C)N[Si](C)(C)CCl SXSNZRHGAMVNJE-UHFFFAOYSA-N 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- CJOCCCWCYHQYPZ-UHFFFAOYSA-N diethoxy(diethyl)stannane Chemical compound CCO[Sn](CC)(CC)OCC CJOCCCWCYHQYPZ-UHFFFAOYSA-N 0.000 description 1
- ADTGAVILDBXARD-UHFFFAOYSA-N diethylamino(dimethyl)silicon Chemical compound CCN(CC)[Si](C)C ADTGAVILDBXARD-UHFFFAOYSA-N 0.000 description 1
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 1
- BXVLQFGQYHYURU-UHFFFAOYSA-N diethyltin Chemical compound CC[Sn]CC BXVLQFGQYHYURU-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- PSPIIGZMTCQLJU-UHFFFAOYSA-N dimethyl-phenyl-(piperazin-1-ylmethyl)silane Chemical compound C=1C=CC=CC=1[Si](C)(C)CN1CCNCC1 PSPIIGZMTCQLJU-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- CKHUMILJZKSHJU-UHFFFAOYSA-N ethane;tin Chemical compound CC[Sn] CKHUMILJZKSHJU-UHFFFAOYSA-N 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- NRHMQDVIKPCCRT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO NRHMQDVIKPCCRT-UHFFFAOYSA-N 0.000 description 1
- XCKWFNSALCEAPW-UHFFFAOYSA-N ethanolate;tin(2+) Chemical compound [Sn+2].CC[O-].CC[O-] XCKWFNSALCEAPW-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- KFLVOKMPRJCQMJ-UHFFFAOYSA-N ethoxy(ethyl)tin Chemical compound CCO[Sn]CC KFLVOKMPRJCQMJ-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- FANAUDUYRDVPHX-UHFFFAOYSA-N ethoxytin Chemical compound CCO[Sn] FANAUDUYRDVPHX-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- QUZPNFFHZPRKJD-UHFFFAOYSA-N germane Chemical compound [GeH4] QUZPNFFHZPRKJD-UHFFFAOYSA-N 0.000 description 1
- 229910052986 germanium hydride Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- UISUQHKSYTZXSF-UHFFFAOYSA-N methanolate;tin(2+) Chemical compound [Sn+2].[O-]C.[O-]C UISUQHKSYTZXSF-UHFFFAOYSA-N 0.000 description 1
- JDQLUYWHCUWSJE-UHFFFAOYSA-N methanolate;titanium(3+) Chemical compound [Ti+3].[O-]C.[O-]C.[O-]C JDQLUYWHCUWSJE-UHFFFAOYSA-N 0.000 description 1
- MZQMPJDMPZAJRF-UHFFFAOYSA-N methoxy(methyl)tin Chemical compound CO[Sn]C MZQMPJDMPZAJRF-UHFFFAOYSA-N 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- ZCSJRGDXLOFDBM-UHFFFAOYSA-N n'-[[dimethyl(phenyl)silyl]methyl]ethane-1,2-diamine Chemical compound NCCNC[Si](C)(C)C1=CC=CC=C1 ZCSJRGDXLOFDBM-UHFFFAOYSA-N 0.000 description 1
- NLSXOLJPOYUIKX-UHFFFAOYSA-N n-(3-trimethylsilylpropyl)butan-1-amine Chemical compound CCCCNCCC[Si](C)(C)C NLSXOLJPOYUIKX-UHFFFAOYSA-N 0.000 description 1
- BAHPBZUWESTFBG-UHFFFAOYSA-N n-(trimethylsilylmethyl)propan-2-amine Chemical compound CC(C)NC[Si](C)(C)C BAHPBZUWESTFBG-UHFFFAOYSA-N 0.000 description 1
- LMBXAKYWWMNNCR-UHFFFAOYSA-N n-[anilino(dimethyl)silyl]aniline Chemical compound C=1C=CC=CC=1N[Si](C)(C)NC1=CC=CC=C1 LMBXAKYWWMNNCR-UHFFFAOYSA-N 0.000 description 1
- BOYBHDHQCOROOJ-UHFFFAOYSA-N n-[butylamino(dimethyl)silyl]butan-1-amine Chemical compound CCCCN[Si](C)(C)NCCCC BOYBHDHQCOROOJ-UHFFFAOYSA-N 0.000 description 1
- FTURFVPIEOKJBC-UHFFFAOYSA-N n-[dimethylamino(diphenyl)silyl]-n-methylmethanamine Chemical compound C=1C=CC=CC=1[Si](N(C)C)(N(C)C)C1=CC=CC=C1 FTURFVPIEOKJBC-UHFFFAOYSA-N 0.000 description 1
- VBYLGQXERITIBP-UHFFFAOYSA-N n-[dimethylamino(methyl)silyl]-n-methylmethanamine Chemical compound CN(C)[SiH](C)N(C)C VBYLGQXERITIBP-UHFFFAOYSA-N 0.000 description 1
- NGAVXENYOVMGDJ-UHFFFAOYSA-N n-[ethylamino(dimethyl)silyl]ethanamine Chemical compound CCN[Si](C)(C)NCC NGAVXENYOVMGDJ-UHFFFAOYSA-N 0.000 description 1
- KNLUHXUFCCNNIB-UHFFFAOYSA-N n-dimethylsilyl-n-methylmethanamine Chemical compound CN(C)[SiH](C)C KNLUHXUFCCNNIB-UHFFFAOYSA-N 0.000 description 1
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 description 1
- IPJPAQIHUIKFLV-UHFFFAOYSA-N n-trimethylsilylaniline Chemical compound C[Si](C)(C)NC1=CC=CC=C1 IPJPAQIHUIKFLV-UHFFFAOYSA-N 0.000 description 1
- FFJKAASRNUVNRT-UHFFFAOYSA-N n-trimethylsilylprop-2-en-1-amine Chemical compound C[Si](C)(C)NCC=C FFJKAASRNUVNRT-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229940110728 nitrogen / oxygen Drugs 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- GPQVVAFBSNIQLX-UHFFFAOYSA-N propan-2-olate;tin(2+) Chemical compound CC(C)O[Sn]OC(C)C GPQVVAFBSNIQLX-UHFFFAOYSA-N 0.000 description 1
- WWFXSPBGYMPHHC-UHFFFAOYSA-N propan-2-yl(propan-2-yloxy)tin Chemical compound CC(C)O[Sn]C(C)C WWFXSPBGYMPHHC-UHFFFAOYSA-N 0.000 description 1
- JTBKFHQUYVNHSR-UHFFFAOYSA-N propan-2-yloxyalumane Chemical compound CC(C)O[AlH2] JTBKFHQUYVNHSR-UHFFFAOYSA-N 0.000 description 1
- MVKUHFGZBFINJS-UHFFFAOYSA-N propan-2-yloxyboron Chemical compound [B]OC(C)C MVKUHFGZBFINJS-UHFFFAOYSA-N 0.000 description 1
- PXDRFTPXHTVDFR-UHFFFAOYSA-N propane;titanium(4+) Chemical compound [Ti+4].C[CH-]C.C[CH-]C.C[CH-]C.C[CH-]C PXDRFTPXHTVDFR-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 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
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000391 spectroscopic ellipsometry Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- KEBMUYGRNKVZOX-UHFFFAOYSA-N tetra(propan-2-yl)silane Chemical compound CC(C)[Si](C(C)C)(C(C)C)C(C)C KEBMUYGRNKVZOX-UHFFFAOYSA-N 0.000 description 1
- REWDXIKKFOQRID-UHFFFAOYSA-N tetrabutylsilane Chemical compound CCCC[Si](CCCC)(CCCC)CCCC REWDXIKKFOQRID-UHFFFAOYSA-N 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- VCZQFJFZMMALHB-UHFFFAOYSA-N tetraethylsilane Chemical compound CC[Si](CC)(CC)CC VCZQFJFZMMALHB-UHFFFAOYSA-N 0.000 description 1
- MNWRORMXBIWXCI-UHFFFAOYSA-N tetrakis(dimethylamido)titanium Chemical compound CN(C)[Ti](N(C)C)(N(C)C)N(C)C MNWRORMXBIWXCI-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 229910000083 tin tetrahydride Inorganic materials 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- YGBFTDQFAKDXBZ-UHFFFAOYSA-N tributyl stiborite Chemical compound [Sb+3].CCCC[O-].CCCC[O-].CCCC[O-] YGBFTDQFAKDXBZ-UHFFFAOYSA-N 0.000 description 1
- BXJWDOYMROEHEN-UHFFFAOYSA-N tributylstibane Chemical compound CCCC[Sb](CCCC)CCCC BXJWDOYMROEHEN-UHFFFAOYSA-N 0.000 description 1
- VCSUQOHFBBQHQV-UHFFFAOYSA-N triethoxy(methyl)stannane Chemical compound CCO[Sn](C)(OCC)OCC VCSUQOHFBBQHQV-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- JNONUPYOIZXSNQ-UHFFFAOYSA-N trimethyl(2-piperidin-1-ylethyl)silane Chemical compound C[Si](C)(C)CCN1CCCCC1 JNONUPYOIZXSNQ-UHFFFAOYSA-N 0.000 description 1
- FLQNGSAFRFEKNU-UHFFFAOYSA-N trimethyl(3-piperidin-1-ylpropyl)silane Chemical compound C[Si](C)(C)CCCN1CCCCC1 FLQNGSAFRFEKNU-UHFFFAOYSA-N 0.000 description 1
- WNHFEQWRHXLCMK-UHFFFAOYSA-N trimethyl(pyrrol-1-yl)silane Chemical compound C[Si](C)(C)N1C=CC=C1 WNHFEQWRHXLCMK-UHFFFAOYSA-N 0.000 description 1
- NQLVIKZJXFGUET-UHFFFAOYSA-N trimethyl(pyrrolidin-1-yl)silane Chemical compound C[Si](C)(C)N1CCCC1 NQLVIKZJXFGUET-UHFFFAOYSA-N 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- YVWPNDBYAAEZBF-UHFFFAOYSA-N trimethylsilylmethanamine Chemical compound C[Si](C)(C)CN YVWPNDBYAAEZBF-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
- H05H1/24—Generating plasma
- H05H1/48—Generating plasma using an arc
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
- H05H1/24—Generating plasma
- H05H1/47—Generating plasma using corona discharges
- H05H1/473—Cylindrical electrodes, e.g. rotary drums
-
- 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
- H10K59/8731—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H2240/00—Testing
- H05H2240/10—Testing at atmospheric pressure
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/311—Flexible OLED
-
- 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
Definitions
- the present invention relates to a method for manufacturing a multi-layer stack structure, the structure comprising in order: a substrate - a barrier layer - an adhesive layer - a barrier layer - a substrate.
- this invention relates to a device, e.g. an OLED device comprising such a multi- layer stack structure.
- the present invention relates to an apparatus for producing a multi-layer stack structure, the apparatus comprising a treatment space with at least two electrodes connected to a plasma control unit for generating an atmospheric pressure glow discharge plasma in the treatment space, and a gas supply device in communication with the treatment space for providing compounds (gases and precursors) in the treatment space.
- a gas-barrier film fabricated by forming a thin metal oxide film of aluminum oxide, magnesium oxide or silicon oxide on the surface of a plastic substrate or a film is widely used for wrapping or packaging articles that require shielding from various gases such as water vapor or oxygen and for wrapping or packaging edibles, industrial articles and medicines for preventing them from being deteriorated.
- the gas-barrier film is being used for substrates for liquid-crystal display devices, solar cells and EL devices.
- a transparent substrate that is being much used for liquid-crystal display devices and EL devices is required to be lightweight and has a large panel and, in addition, it is further required to satisfy high-level performance ability in that it has long-term reliability and has a lot of latitude in designing its shape and that it enables curved-face display.
- a film substrate of transparent plastics or the like is being used in place of a glass substrate that is heavy and readily cracked or broken and hardly worked into a large-size panel.
- the film substrate of transparent plastics or the like satisfies the above-mentioned requirements and since it is applicable to a roll-to-roll system, it is more advantageous than glass in that the producibility with it is high and the production cost with it is low.
- the film substrate of transparent plastics or the like is problematic in that its gas-barrier property is not good as compared with that of glass.
- a substrate having a poor gas-barrier property When a substrate having a poor gas-barrier property is used, water vapor and air may penetrate through it; and, for example, when it is used in liquid-crystal display devices, the liquid crystal in the liquid-crystal cell may be degraded and the degraded part may be a display failure, thereby worsening the display quality of the devices. It is known to form a thin metal oxide film on the above-mentioned film substrate, thereby using the resulting gas-barrier film as a transparent substrate.
- a gas-barrier film for use in wrapping materials and liquid-crystal display devices there are known a plastic film coated with silicon oxide through vapor deposition (for example, see JP-4904169 , pp.
- the substrate temperature is limited in layer formation thereon, and therefore a barrier layer having a sufficiently dense and tight structure could not be formed, and a film having a satisfactory barrier property capable of satisfying the requirements could not as yet be formed.
- a silicon nitride and a silicon oxinitride are used, and laminating them is tried.
- US6,413,645 Bl p. 4 [2-54] to p. 8 [8-22]
- US6,413,645 Bl p. 4 [2-54] to p. 8 [8-22]
- a barrier film fabricated by laminating, on a substrate film, two layers of a silicon oxinitride having a different nitrogen/oxygen constitution ratio.
- the constitution could not satisfy both a sufficient gas- barrier level and a bending resistance which the film substrate must have in its use, and further technical improvement on it is desired.
- a technique of producing a barrier film having an alternate laminate structure of an organic layer/inorganic layer according to a vacuum evaporation method is proposed (for example, see Affinito et al. , Thin Solid Films, 1996, P. 290-291 (pp. 63-67 )), and it gives a barrier film useable as for a film substrate for organic EL devices.
- the adhesiveness between the organic layer and the inorganic layer is not always satisfactory, and a multi-layered structure of at least 6 layers is needed for providing a high-reliability barrier film for organic EL devices.
- the present invention provides an effective, efficient and cheap process for manufacturing of flexible multi-layer material with excellent barrier property to water vapour. Furthermore, this invention provides flexible multi-layer material with an excellent barrier property to water vapour.
- a method as described in the introduction above comprising: a) providing two substrates in a single treatment space, the single treatment space being formed between at least two electrodes for generating an atmospheric pressure glow discharge plasma in the single treatment space; b) treating the facing surfaces of the two substrates simultaneously in the single treatment space; c) laminating the two treated substrates with an adhesive layer in between the facing surfaces to obtain the multi-layer stack structure.
- the present method may be applied to improve certain characteristics when applying layers of material to the two substrates (films or foils) and after laminating these into one multi-layer stack structure (again a roll of film or foil).
- Using the present invention embodiments allows to provide for deposition rates of more than 1 nm/s, e.g. 5 nm/s or even 10nm/s.
- the method further comprises laminating two or more multi-layer stack structures with an additional adhesive layer in between.
- the WVTR characteristics may be even further improved.
- the substrates are provided as sheets to obtain the multi-layer stack structure in a continuous process.
- the substrates may be provided from two rolls with a predetermined width, and the laminated structure may be spooled on a receiving roll. This two roll to one roll process is very efficient for continuous manufacturing of the multi-layer stack structure, by adhering the two treated substrates with the treated surfaces facing each other by lamination into one roll using an adhesive.
- the substrates are organic resin films.
- organic resin films examples include, but are not limited to PEN (PolyEthylene Naphtalate), PET (PolyEthylene Teraphtalate), PC (PolyCarbonate), COP (Cyclic Olefin Polymer), COC (Cyclic Olefin CoPolymer), etc.
- the thickness of the substrates may be between 20 and 800 ⁇ m, e.g. 50 ⁇ m or 200 ⁇ m.
- the step of treating the facing surfaces comprises in a further embodiment depositing an inorganic material on the substrate surface to form the barrier layer, e.g. an SiOx layer.
- the step of treating the facing surfaces is executed with a duty cycle above 10%, preferably above 60%. This effectively reduces the formation of dust when depositing the inorganic layer on the substrates.
- An atmospheric pressure glow discharge is generated in a further embodiment by applying electrical power from a power supply to the at least two electrodes in the treatment space during an on-time (t on ), the treatment space being filled with a gas composition, including a precursor of the chemical compound or element to be deposited, wherein the gas composition comprises an amount of nitrogen between 1 and 99.99% and an amount of oxygen between 0.01 and 25%. Again, this reduces the chance of formation of dust in the deposition step and an improvement of the quality of the deposited layer.
- the present invention relates to a device comprising a multilayer structure obtained according to the present method embodiments, e.g. an OLED device.
- the present the present invention relates to an apparatus as defined in the introduction above, in which the treatment space is a single treatment space formed between the at least two electrodes, and the apparatus further comprising a feeder system for providing two substrates simultaneously in the single treatment space for treatment using the generated atmospheric pressure glow discharge plasma, and a laminating system for laminating the two treated substrates with an adhesive layer in between.
- Fig. 1 shows a schematic view of a plasma generation apparatus in which the present invention may be embodied
- Fig. 2 shows a plot of a periodic signal generated by the power supply to feed the electrodes of the plasma generation of apparatus of Fig. 1;
- Fig. 3 shows a schematic view of an embodiment involving a 2-rolls-to-l-roll process
- Fig. 4a and 4b shows cross sectional views of structures according to embodiments of the present invention.
- FIG. 1 shows a schematic view of a plasma apparatus 10 in which the present invention may be applied.
- a treatment space 5, which may be a treatment chamber within an enclosure 7, or a treatment space 5 with an open structure, comprises two curved electrodes 2, 3, e.g. cylinder electrodes.
- the electrodes 2, 3 are provided with a dielectric barrier in order to be able to generate and sustain a glow discharge at atmospheric pressure in the treatment space 5.
- a plurality of electrodes 2, 3 is provided.
- the electrodes 2, 3 may be mounted to allow rotation in operation, e.g. using a mounting shaft and/or bearing arrangements.
- the electrode 2, 3 may be provided as a rolling electrode 2, 3 which is freely rotating or may be driven at certain angular speed using controller and drive units (which as such are known to the skilled person).
- Two substrates 6a, 6b may be treated in the single treatment space 5 simultaneously, effectively enhancing the throughput of the plasma apparatus 10.
- the substrates 6a, 6b may be provided in the treatment space 5 from a respective roll 4, allowing a continuous feed of the substrates 6a, 6b to the treatment space 5.
- Treated substrates 6a', 6b' leave the treatment space 5 for further processing or e.g. for storage. Treating the two substrates 6a, 6b in the same treatment space 5 simultaneously provides a more uniform plasma treatment as compared to the application of using separate treatment processes for each substrate 6a, 6b.
- the formation of a glow discharge plasma may be stimulated by controlling the displacement current (dynamic matching) using a plasma control unit 11 connected to the electrodes 2, 3, leading to a uniform activation of the surface of substrate 6a, 6b in the treatment space 5.
- the plasma control unit 11 e.g. comprises a power supply and associated control circuitry as described in the pending international patent application PC17NL2006/050209, and European patent applications EP-A-1381257, EP-A- 1626613 of applicant, which are herein incorporated by reference.
- the invention further relates to a method of manufacturing a multi-layer stack structure (e.g. on the surface of substrate 6a, 6b as shown in Fig. 1) providing an excellent permeation barrier to water vapour to be used in several different devices. Furthermore, the invention relates to a multi-layer structure providing excellent barrier properties against water vapour.
- a first measurement is done using the Mocon Aquatran which uses a coloumbmetric cell (electrochemical cell) with a minimum detection limit of 5*10 ⁇ 4 g/m 2 .day.
- This method provides a more sensitive and accurate permeability evaluation than the permeation measurement by using IR absorption (known to the person skilled in the art).
- Measurement conditions can be varied from 10-40 0 C and also relative humidity usually from 60-90%.
- optical density (OD) of a film is proportional to the thickness so we can calculate the WVTR via the following equation:
- A is the scaling factor between calcium thickness and OD
- M[H20], and M[Ca] are the molar masses of water and Ca with values of 18 and 40.1 units respectively
- pc a is the density of calcium
- Lc a and Wc a are the length and width of the deposited Ca
- Ls and Ws are the length and width of the permeation area defined by the interior boundary
- d(OD)/dt is the slope of the measured optical absorbance versus time.
- this multi-layer stack structure 12 can be used as over- and/or underlayer material protecting and/or enveloping organic light emitting diode (OLED) devices.
- OLED organic light emitting diode
- a combination of gasses is introduced from a gas supply device 8, including a pre-cursor.
- the gas supply device 8 may be provided with storage, supply and mixing components as known to the skilled person.
- the purpose is to have the precursor decomposed in the treatment space 5 to a chemical compound or chemical element which is deposited on the surfaces of the two substrates 6a, 6b.
- the combination of gases comprises besides the precursor an active gas like for example oxygen and a mixture of inert gases.
- an active gas like for example oxygen
- a mixture of inert gases When using such embodiments in general dust formation is observed after very short deposition times and a smooth dust- free deposition cannot be obtained.
- Pulsing the power is another standard way to diminish the plasma reactivity by decreasing the average energy transferred to the plasma per unit of time.
- the standard method for suppression of dust formation is based on the fast decay of dust coagulation centres during the power off- time of the plasma. This can be regarded as a "natural death" of dust during the plasma off-time.
- the duty cycle defined as the power on time divided by the sum of the power on and power of time of these pulsing examples is large, typically in the range of 50-98 %. Pulsing the plasma with an off-time of a few milliseconds is enough to interrupt the growth of dust particles and to limit thus the dust formation.
- the present invention is not based on the "natural dead” (decay) of dust coagulation centers but on minimizing their density in plasma so from the stage of Power on-time.
- standard method which is a manipulation of dust formation based on the decay of coagulation centers via adjustment of Power off-time this is rather a method based on preventing from the beginning the formation of the coagulation centers.
- HMDSO hexamethyldisiloxane
- the gas composition comprises oxygen and nitrogen.
- Oxygen can be used for example from 0.01 to 25% of the gas composition and the gas composition can further comprise nitrogen in an amount from 99.99% to 1%.
- the gas composition may comprise a noble gas like helium, neon or argon.
- the amount of the noble gas used can range from 1% to as high as 90 % of the total gas composition. Even a value of more than 95% for example 99% can be used.
- the total gas composition including the precursor amount would be oxygen in an amount ranging from 0.01 to 25% and noble gas nitrogen mixture ranging from 99.99% until 75 % with the amounts of nitrogen and noble gas as identified above.
- argon as noble gas, very good results have been obtained.
- Embodiments using only nitrogen as the inert gas besides the active gas can also advantageously be used.
- the power supply may be arranged to provide a periodic electrical signal with an on-time (t on ) and an off- time (toff), the sum of the on-time and off-time being the period or cycle of the periodic electrical signal.
- the on-time may vary from very short, e.g. 20 ms, to short, e.g. 500 ms. Because of the beneficial effect of nitrogen also an on-time of more than 500ms can be used, for example Is.
- the on-time effectively results in a pulse train having a series of sine wave periods at the operating frequency, with a total duration of the on-time (e.g. 10 to 30 periods of a sine wave) of 0.1 to 0.3 ms. This is schematically shown in the graph of Fig. 2.
- very short pulses are used in order to prevent the dust formation.
- the dust formation is even further suppressed, while the deposition rate is kept at a high level because through the use of the gas compositions specified above a duty cycle of more than 10 % can be realised.
- the power on- time of the APG plasma is short enough not to cause additional charging of the reactive species, thus allowing a much more effective deposition process.
- Pulsing the plasma with an off-time in the order of milliseconds is enough to interrupt the growth of dust particles and to limit thus the dust formation.
- an interval between pulses (Wf) in the order of the time of residence of the gas in the treatment space 5 of a reactor can also advantageously be used in the present invention.
- the time between pulses should be comparable to the residence time of the gas in the discharge space.
- argon/oxygen/HMDSO for example there are reactive species with a longer lifetime which need to be flushed before the start of the next pulse.
- the residence time can be enlarged to values which are higher than the cycle time. Residence times as high as 10 times the cycle times might be used in these embodiments.
- the proposed pulsed plasma method is based on the suppression of formation of the dust coagulation centers from the initial phase during the power on-time ton. Furthermore, it is based on the decay of the dust coagulation centers by adjusting the power off-time (W f ) and by adjusting the gas composition.
- the total amount of coagulation centers seem to be determined by the amount of the precursor of the chemical compound or chemical element to be deposited in the plasma gas composition, and the gas mixture used, for example the percentage of oxygen and of course the gas flow as discussed above. In case the precursor amount in the gas mixture is reduced and/or the amount of reactive gas like oxygen, the amount of coagulation centers in the plasma gas will also be reduced. Reducing the precursor amount in the gas composition will off course influence the efficiency of the deposition process. Best results are obtained in general with a precursor concentration from 2 to 500 ppm of the gas composition and for example an oxygen concentration of e.g. 0.01% of the gas phase, or more, e.g. 2%, but less than 25% for example 10%.
- an efficient way of controlling the generation of dust coagulation centers may be accomplished by having the power supply operate at a duty cycles in general from more than 1% or more than 5% for example 10%, 20%, 30%, 40%, 50%, 60% and even 98%, with short power on- times in the order of 0.05-0.5 ms.
- the power on-time (t on ) and power off-time (Wf) can be adjusted in order to maintain a large density of reactive radicals and an efficient deposition process but within the limits imposed by the above mentioned conditions.
- oxygen as a reactive gas in this invention has a many advantages also other reactive gases might be used like for example hydrogen, carbon dioxide, ammonia, oxides of nitrogen, and the like.
- precursors can be can be selected from (but are not limited to): W(CO)6, Ni(CO)4, Mo(CO)O, Co2(CO)8, Rh4(CO)12, Re2(CO)10, Cr(CO)6, or Ru3(CO)12 , Tantalum Ethoxide (Ta(OC2H5)5), Tetra Dimethyl amino Titanium (or TDMAT) SiH4 CH4 , B2H6 or BC13 , WF6 , TiC14, GeH4,
- the precursors are used in a concentration of 2-500 ppm e.g. around 50 ppm of the total gas composition.
- the plasma gas including the precursor to be deposited via atmospheric pressure glow discharge plasma is brought into contact with two resin substrate 6a, 6b rolls synchronously via one device as can be seen in Fig. 1.
- This step will result in less consumption of precursor and/or carrier materials and as such to much more efficient application of plasma gas including precursor to be used onto the substrates 6a, 6b, which is from economical point and commercialization of view preferred.
- the figure is only illustrative for plasma gas contacting two rolls of resins synchronously, it may be understood that the method may include also the use of a remote plasma device and jetting the plasma gas including the precursor element to be deposited onto the 2 resin rolls synchronously.
- atmospheric pressure glow discharge avoids the use of complex and expensive vacuum equipment which is preferred in order to make the process simpler and more cost-effective. Although the mechanism is not quite understood we believe that this improvement is related to far much better uniform and dense deposition of precursor element related to the use of our atmospheric pressure discharge.
- an inorganic barrier 14 is formed with a thickness of 10 nm to l ⁇ m, preferably 20 nm to 300 nm and more preferably 50 nm to 200 nm.
- Each inorganic barrier layer will display typically a water vapour transmission rate (WVTR) of about 0.03 g/m .day before the lamination step of this invention, which lamination step is described in more detail below using the embodiment of Fig. 3.
- WVTR water vapour transmission rate
- Fig. 3 the lamination process is shown according an embodiment of this invention.
- the pair of inorganic barrier layers 6a', 6b' are suitably bonded or laminated together with an adhesive 15 on the inorganic barrier 14 side facing each other. In the embodiment shown in Fig. 3 this is accomplished by first forming two substrates 6a', 6b' with an inorganic barrier layer 14 in a single treatment space 5, similar to the embodiment of Fig. 1.
- the treated substrates 6a', 6b' are then fed to two laminating rollers 21, 22, and an adhesive material is applied the to inorganic layer side of substrates 6a', 6b' using an adhesive applicator 20.
- the laminating rollers 21, 22 are arranged to provide heat or radiation to the adhesive material between the treated substrates 6a', 6b', in order to cure or modify the adhesive material to form an adhesive layer 15.
- a multi layer stack structure 12 is obtained having an excellent barrier for water vapour.
- already excellent barrier properties were observed in the case when one [resin layer-inorganic] -layer stack combination 6a is adhered to another one [inorganic-organic]-layer stack combination 6b using an adhesive 15 between the two opposing face related inorganic barrier coatings 14 resulting in a multi layer stack structure 12 comprising the following layers as shown in cross section in Fig. 4a: i) organic resin (substrate 6a); ii) an inorganic barrier 14; iii) an adhesive 15; iv) an inorganic barrier 14 and v) an organic resin (substrate 6b). Also indicated are the semi-products 6a', 6b' each comprising a substrate 6a, 6b and a barrier layer 14.
- the laminate structure may display a typical water vapour transmission rate (WVTR) of 7*10 "4 g/m 2 .day.
- WVTR water vapour transmission rate
- a further product multi-layer stack structure 12 can be prepared by using each produced multi- layer stack structure 12 as a starting substrate roll(s) in another separate 2 roll-to- 1 roll operation step.
- the separate structures 12 are laminated using an additional adhesive layer 16 as shown in the cross sectional view of Fig. 4b.
- a thicker multi-stack layer structure comprising i) [organic resin-inorganic barrier- adhesive- inorganic barrier- organic resin layer-adhesive] n layers and ii) [organic resin- inorganic barrier- adhesive- inorganic barrier-organic resin layer], layer where n is an integer larger than 0.
- n is an integer larger than 0.
- Adhesives 15, 16 that may be applied for bonding the inorganic barrier layers 14 include all suitable thermoplastic-and elasto-plastic polymers; polymers which are curable by radiation such as by ultraviolet or electron-beam, by heat, by chemical initiators or by combinations thereof; organic or organic-containing adhesives, such as acrylics, urethanes, epoxides, polyolefins, organosilicones and others; and products of plasma-polymerization, oligomerization, or curing of organic-, organosilicon and other organometallic compounds, either volatile or deposited by other means such as spraying, sputtering, casting or dip-coating.
- the adhesive forms an adhesive layer 15 bonding the two opposing faces of inorganic barrier layers 14 in the embodiment of Fig. 4a and an additional adhesive layer 16 bonding two substrates 6a, 6b of different multi-layer stack structures 12 in the embodiment of Fig. 4b.
- the adhesive layer 15, 16 may suitably have a thickness of 50 nm to 1000 ⁇ m, preferably from 100 nm to 100 ⁇ m.
- the multi-layer stack structures 12 may be applied in several devices as under-or over-layer protection means. Preferred use of these multi-layers is in protecting OLEDs by using these multi-layers enveloping the OLED-devices.
- the multi-layer material (single or multiple multi-layer stack structures 12) according to the invention may be used also in other types of devices, such as liquid crystal displays or in organic photovoltaic devices, which are known in prior art to require transparent materials impermeable to oxygen and water vapour.
- WVTR of the PEN substrate without coating was quantified by Mocon Aquatran and is typically 0.27+/-0.03 g/m2.day .
- Comparitive example Typically 100 nm thick inorganic layers were deposited on optical grade PEN sheets using a low vacuum ICP plasma enhanced CVD process using argon, HMDSO and oxygen. The layer thickness of 100 nm SiO 2 was quantified by Spectroscopic Ellipsometry (Woollam M-2000) and the WVTR was quantified by Mocon Aquatran. The WVTR of the barrier samples was typically 0.1g/m 2 .day (at 2OC and 60%RH). Subsequently two barrier films were laminated face to face (barrier to barrier) using a test-laminator with a UV curable hydrophobic acrylate and UV-cured. The acrylate layer has a thickness of typically 10 micron.
- the WVTR is measured of the laminate structure using the Mocon Aquatran.
- the WVTR obtained is typically 0.01 g/m 2 .day.
- Two barrier films 14 of 50 nm thick are deposited synchronously using the electrode set-up as shown in Fig. 1 using an atmospheric pressure plasma device 10.
- a SiOx layer 14 is deposited on both sides of the substrates 6a, 6b facing the plasma discharge.
- the two substrates 6a', 6b' are brought together and laminated with the same hydrophobic acrylate as above with a thickness of 10 micron followed by UV-curing. Under the same conditions more barrier samples are produced and part of this material is prepared for permeability characterization by Mocon.
- the WVTR of the individual layers 6a', 6b' is typically 0.03 g/m 2 .day, whereas the permeability of the laminate structure 12 is typically less than 1*10 ⁇ 3 g/m 2 .day.
- Two barrier films 14 of 100 nm thick are deposited in one time using the electrode set-up as shown in Fig. 1.
- a SiOx layer 14 is deposited on both sides of the substrates 6a, 6b facing the plasma discharge.
- the two substrates 6a', 6b' are brought together and laminated using the same thickness and same acrylate layer 15.
- WVTR of the individual layers 6a', 6b' is typically 0.03 g/m 2 .day, whereas the permeability of the laminate structure 12 is below the detection limit of the Mocon
- the permeability is characterized by the calcium corrosion test.
- This method allows characterization of the average WVTR as low as 10 ⁇ 5 to 10 ⁇ 6 g/m 2 .day at 4O 0 C / 90%RH.
- the WVTR for the multi-layer stack structure 12 was found to be typically in the order of 10 ⁇ 4 g/m 2 .day.
- the method can be used too to evaluate defect resolved calcium corrosion. By repeatedly measuring the development of the defects it was observed by optical microscopy that very small defects tend to appear after more than 500 hours. However, defects remain very small, i.e. there is no growth of the defects and as a matter of fact defects remain so small that they are not visible by naked eye.
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
- Laminated Bodies (AREA)
- Electroluminescent Light Sources (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
Abstract
A method and apparatus for manufacturing a multi-layer stack structure (12), the structure (12) comprising in order: a substrate (6a) a barrier layer (14) an adhesive layer (15) a barrier layer (14) a substrate (6b). The method comprises: a) providing two substrates (6a, 6b) in a single treatment space (5), the treatment space (5) comprising at least two electrodes (2, 3) for generating an atmospheric pressure glow discharge plasma in the treatment space(5); b) treating the facing surfaces of the two substrates (6a, 6b) simultaneously in the single treatment space (5); c) laminating the two treated substrates (6a, 6b) with an adhesive layer (15) in between the facing surfaces to obtain the multi-layer stack structure (12).
Description
METHOD FOR MANUFACTURING A MULTI LAYER STACK STRUCTURE WITH IMPROVED WVTR BARRIER PROPERTY
TECHNICAL FIELD The present invention relates to a method for manufacturing a multi-layer stack structure, the structure comprising in order: a substrate - a barrier layer - an adhesive layer - a barrier layer - a substrate.
Furthermore, this invention relates to a device, e.g. an OLED device comprising such a multi- layer stack structure. In an even further aspect, the present invention relates to an apparatus for producing a multi-layer stack structure, the apparatus comprising a treatment space with at least two electrodes connected to a plasma control unit for generating an atmospheric pressure glow discharge plasma in the treatment space, and a gas supply device in communication with the treatment space for providing compounds (gases and precursors) in the treatment space.
BACKGROUND ART
International patent application WO99/04411 discloses plasma treatment systems and treatment methods, in which a substrate web is treated using cylindrical cavity electrodes. Direct plasma treatment and remote plasma treatment arrangements are disclosed. Treating two substrate surfaces simultaneously is performed using two different plasma treatment arrangements in a single enclosure (see embodiment of Fig. 13).
Heretofore, a gas-barrier film fabricated by forming a thin metal oxide film of aluminum oxide, magnesium oxide or silicon oxide on the surface of a plastic substrate or a film is widely used for wrapping or packaging articles that require shielding from various gases such as water vapor or oxygen and for wrapping or packaging edibles, industrial articles and medicines for preventing them from being deteriorated. Apart from its applications for wrapping and packaging articles, in addition, the gas-barrier film is being used for substrates for liquid-crystal display devices, solar cells and EL devices. In particular, a transparent substrate that is being much used for liquid-crystal display devices and EL devices is required to be lightweight and has a large panel and, in addition, it is further required to satisfy high-level performance ability in that it has
long-term reliability and has a lot of latitude in designing its shape and that it enables curved-face display.
Recently, in the field of liquid-crystal display devices and EL devices, a film substrate of transparent plastics or the like is being used in place of a glass substrate that is heavy and readily cracked or broken and hardly worked into a large-size panel. In addition, since the film substrate of transparent plastics or the like satisfies the above-mentioned requirements and since it is applicable to a roll-to-roll system, it is more advantageous than glass in that the producibility with it is high and the production cost with it is low. However, the film substrate of transparent plastics or the like is problematic in that its gas-barrier property is not good as compared with that of glass. When a substrate having a poor gas-barrier property is used, water vapor and air may penetrate through it; and, for example, when it is used in liquid-crystal display devices, the liquid crystal in the liquid-crystal cell may be degraded and the degraded part may be a display failure, thereby worsening the display quality of the devices. It is known to form a thin metal oxide film on the above-mentioned film substrate, thereby using the resulting gas-barrier film as a transparent substrate. As a gas-barrier film for use in wrapping materials and liquid-crystal display devices, there are known a plastic film coated with silicon oxide through vapor deposition (for example, see JP-4904169 , pp. 1-3), and a plastic film coated with aluminium oxide through vapor deposition (for example, see JP-A-58-217344, pp. 1-4). These have a water- vapor barrier level of about 1 g/m .day. However, with recent development of large-panel liquid-crystal display devices and high-definition display devices, the film substrate is being required to have a water- vapor barrier level of about 0.1 g/m .day. Recently, the development of organic EL devices and high-definition color liquid-crystal display devices that are required to have a higher gas-barrier level is being further promoted, and a substrate that keeps a transparency applicable to them and has a higher gas-barrier level, especially a higher water- vapor barrier level of not more than 0.01 g/m2. day is being required.
To satisfy these requirements, some methods expected to produce a higher gas- barrier level have been investigated, for example, a sputtering method of forming a thin film by the use of a plasma generated through glow discharge under low pressure, and a CVD method for film formation. In addition, an attempt to change laminate structure
formation to attain a desired result is tried (for example, see JP-A-2003-206361, pp. 2-3).
However, when a film substrate is used, the substrate temperature is limited in layer formation thereon, and therefore a barrier layer having a sufficiently dense and tight structure could not be formed, and a film having a satisfactory barrier property capable of satisfying the requirements could not as yet be formed.
As a thin- film material having a good barrier property, a silicon nitride and a silicon oxinitride are used, and laminating them is tried. For example, US6,413,645 Bl (p. 4 [2-54] to p. 8 [8-22]) describes a barrier film fabricated by laminating, on a substrate film, two layers of a silicon oxinitride having a different nitrogen/oxygen constitution ratio. However, the constitution could not satisfy both a sufficient gas- barrier level and a bending resistance which the film substrate must have in its use, and further technical improvement on it is desired.
On the other hand, a technique of producing a barrier film having an alternate laminate structure of an organic layer/inorganic layer according to a vacuum evaporation method is proposed (for example, see Affinito et al. , Thin Solid Films, 1996, P. 290-291 (pp. 63-67 )), and it gives a barrier film useable as for a film substrate for organic EL devices.
However, the adhesiveness between the organic layer and the inorganic layer is not always satisfactory, and a multi-layered structure of at least 6 layers is needed for providing a high-reliability barrier film for organic EL devices.
Another method is described in international patent publication WO03/005461 wherein two polymer- inorganic multi-layer materials in opposed facing relationship are sandwiched displaying good barrier properties. The deposition of the inorganic layer is done in very complicated vacuum pressure plasma process in order to suppress contaminations and defects.
In the art of manufacturing and commercialization of flexible thin substrate material for OLED devices displaying excellent barrier properties a more cost-effective and a simpler process are desired.
DISCLOSURE OF THE INVENTION
The present invention provides an effective, efficient and cheap process for manufacturing of flexible multi-layer material with excellent barrier property to water
vapour. Furthermore, this invention provides flexible multi-layer material with an excellent barrier property to water vapour.
In accordance with one aspect of the invention there is provided a method as described in the introduction above, the method comprising: a) providing two substrates in a single treatment space, the single treatment space being formed between at least two electrodes for generating an atmospheric pressure glow discharge plasma in the single treatment space; b) treating the facing surfaces of the two substrates simultaneously in the single treatment space; c) laminating the two treated substrates with an adhesive layer in between the facing surfaces to obtain the multi-layer stack structure.
By simultaneously treating two substrates in the single treatment space and subsequent laminating of the two substrates, a very efficient production process is obtained resulting in a multi-layer stack structure having very good water vapour transmission rate characteristics. Furthermore, the chance of impurities or other contaminations reaching the substrates before laminating is reduced. Also, a more uniform treatment of the substrates is achieved when using a single treatment space. It has been found that the present method may be applied to improve certain characteristics when applying layers of material to the two substrates (films or foils) and after laminating these into one multi-layer stack structure (again a roll of film or foil). Using the present invention embodiments allows to provide for deposition rates of more than 1 nm/s, e.g. 5 nm/s or even 10nm/s.
In a further embodiment, the method further comprises laminating two or more multi-layer stack structures with an additional adhesive layer in between. By further stacking multi-layer stack structures, the WVTR characteristics may be even further improved.
The substrates are provided as sheets to obtain the multi-layer stack structure in a continuous process. For example, the substrates may be provided from two rolls with a predetermined width, and the laminated structure may be spooled on a receiving roll. This two roll to one roll process is very efficient for continuous manufacturing of the multi-layer stack structure, by adhering the two treated substrates with the treated surfaces facing each other by lamination into one roll using an adhesive.
In a further embodiment, the substrates are organic resin films. Examples of such organic resin films (of polymer materials) include, but are not limited to PEN (PolyEthylene Naphtalate), PET (PolyEthylene Teraphtalate), PC (PolyCarbonate), COP (Cyclic Olefin Polymer), COC (Cyclic Olefin CoPolymer), etc. The thickness of the substrates may be between 20 and 800 μm, e.g. 50 μm or 200 μm.
The step of treating the facing surfaces comprises in a further embodiment depositing an inorganic material on the substrate surface to form the barrier layer, e.g. an SiOx layer.
In a further embodiment, the step of treating the facing surfaces is executed with a duty cycle above 10%, preferably above 60%. This effectively reduces the formation of dust when depositing the inorganic layer on the substrates.
An atmospheric pressure glow discharge is generated in a further embodiment by applying electrical power from a power supply to the at least two electrodes in the treatment space during an on-time (ton), the treatment space being filled with a gas composition, including a precursor of the chemical compound or element to be deposited, wherein the gas composition comprises an amount of nitrogen between 1 and 99.99% and an amount of oxygen between 0.01 and 25%. Again, this reduces the chance of formation of dust in the deposition step and an improvement of the quality of the deposited layer. In a further aspect, the present invention relates to a device comprising a multilayer structure obtained according to the present method embodiments, e.g. an OLED device.
In an even further aspect, the present the present invention relates to an apparatus as defined in the introduction above, in which the treatment space is a single treatment space formed between the at least two electrodes, and the apparatus further comprising a feeder system for providing two substrates simultaneously in the single treatment space for treatment using the generated atmospheric pressure glow discharge plasma, and a laminating system for laminating the two treated substrates with an adhesive layer in between.
SHORT DESCRIPTION OF THE FIGURES
The present invention will be discussed in more detail below, using a number of exemplary embodiments, with reference to the attached drawings, in which
Fig. 1 shows a schematic view of a plasma generation apparatus in which the present invention may be embodied; Fig. 2 shows a plot of a periodic signal generated by the power supply to feed the electrodes of the plasma generation of apparatus of Fig. 1;
Fig. 3 shows a schematic view of an embodiment involving a 2-rolls-to-l-roll process; and
Fig. 4a and 4b shows cross sectional views of structures according to embodiments of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Fig. 1 shows a schematic view of a plasma apparatus 10 in which the present invention may be applied. A treatment space 5, which may be a treatment chamber within an enclosure 7, or a treatment space 5 with an open structure, comprises two curved electrodes 2, 3, e.g. cylinder electrodes. In general the electrodes 2, 3 are provided with a dielectric barrier in order to be able to generate and sustain a glow discharge at atmospheric pressure in the treatment space 5. Alternatively, a plurality of electrodes 2, 3 is provided. The electrodes 2, 3 may be mounted to allow rotation in operation, e.g. using a mounting shaft and/or bearing arrangements. The electrode 2, 3 may be provided as a rolling electrode 2, 3 which is freely rotating or may be driven at certain angular speed using controller and drive units (which as such are known to the skilled person). Two substrates 6a, 6b may be treated in the single treatment space 5 simultaneously, effectively enhancing the throughput of the plasma apparatus 10. The substrates 6a, 6b may be provided in the treatment space 5 from a respective roll 4, allowing a continuous feed of the substrates 6a, 6b to the treatment space 5. Treated substrates 6a', 6b' leave the treatment space 5 for further processing or e.g. for storage. Treating the two substrates 6a, 6b in the same treatment space 5 simultaneously provides a more uniform plasma treatment as compared to the application of using separate treatment processes for each substrate 6a, 6b.
The formation of a glow discharge plasma may be stimulated by controlling the displacement current (dynamic matching) using a plasma control unit 11 connected to
the electrodes 2, 3, leading to a uniform activation of the surface of substrate 6a, 6b in the treatment space 5. The plasma control unit 11 e.g. comprises a power supply and associated control circuitry as described in the pending international patent application PC17NL2006/050209, and European patent applications EP-A-1381257, EP-A- 1626613 of applicant, which are herein incorporated by reference.
The invention further relates to a method of manufacturing a multi-layer stack structure (e.g. on the surface of substrate 6a, 6b as shown in Fig. 1) providing an excellent permeation barrier to water vapour to be used in several different devices. Furthermore, the invention relates to a multi-layer structure providing excellent barrier properties against water vapour.
In order to quantify water vapour transmission rates for barrier films two different measurements may be used. A first measurement is done using the Mocon Aquatran which uses a coloumbmetric cell (electrochemical cell) with a minimum detection limit of 5*10~4 g/m2.day. This method provides a more sensitive and accurate permeability evaluation than the permeation measurement by using IR absorption (known to the person skilled in the art). Measurement conditions can be varied from 10-40 0C and also relative humidity usually from 60-90%.
Secondly, to perform even more sensitive permeation measurements a calcium corrosion test was carried out under the conditions of 4O0C and 90%RH. Basically, calcium is evaporated on a test substrate and then a glass slide is attached to cover the calcium layer. Then this obtained sample is exposed to 4O0C and 90%RH, while monitoring the light absorption from the sputtered calcium layer.
The optical density (OD) of a film is proportional to the thickness so we can calculate the WVTR via the following equation:
- _o A : M[H2O] ^ LCaWCa d(OD)
WVTR = -2 A L 2 J pc
M[Ca] Ca LsWs dt
where A is the scaling factor between calcium thickness and OD, M[H20], and M[Ca] are the molar masses of water and Ca with values of 18 and 40.1 units respectively, pca is the density of calcium, Lca and Wca are the length and width of the deposited Ca, Ls and Ws are the length and width of the permeation area defined by the interior boundary, d(OD)/dt is the slope of the measured optical absorbance versus time.
Surprisingly, it has been observed that after i) deposition of an inorganic barrier layer (e.g. SiO2) on the two organic resin (e.g. PE) substrates 6a/6b as shown schematically in Fig. 1 by using an atmospheric pressure glow discharge plasma in one treatment space 5, in which an atmospheric pressure glow discharge is generated by applying electrical power from a power supply 11 to at least two electrodes 2, 3 in the treatment space 5, the treatment space 5 being filled with a gas composition, including a precursor of the chemical compound or element to be deposited, wherein the gas composition comprises an amount of nitrogen between 1 and 99.99% and an amount of oxygen between 0.01 and 25% and after ii) lamination of the two rolls of [resin- inorganic barrier] -layers 6a, 6b with an adhesive 15, it is possible to prepare a multilayer stack structure 12 with far better water vapour barrier properties when using of a plasma deposition process in vacuum. This is described in more detail with reference to Fig. 3 below.
In particular this multi-layer stack structure 12 can be used as over- and/or underlayer material protecting and/or enveloping organic light emitting diode (OLED) devices.
In the treatment space 5, a combination of gasses is introduced from a gas supply device 8, including a pre-cursor. The gas supply device 8 may be provided with storage, supply and mixing components as known to the skilled person. The purpose is to have the precursor decomposed in the treatment space 5 to a chemical compound or chemical element which is deposited on the surfaces of the two substrates 6a, 6b.
In general the combination of gases comprises besides the precursor an active gas like for example oxygen and a mixture of inert gases. When using such embodiments in general dust formation is observed after very short deposition times and a smooth dust- free deposition cannot be obtained. In plasmas used for high quality applications
(microelectronics, permeation barrier, optical applications) dust formation is a serious concern. For such applications the dust formation can compromise the quality of the coating. At atmospheric pressure dust formation is a common fact, due to the typical large power density of the plasma and large concentrations of reactive molecules. For this reason the industrial use of atmospheric plasmas for coating applications is presently limited to low-end applications such as increasing adhesion. With respect to the mechanism of dust formation in plasma at atmospheric pressure, it is assumed that the clustering seeds for dust formation are negative and positive ions formed by the
dissociation of reactive molecules. In order to prevent dust formation it is necessary to limit the dissociation of molecules by plasma in order to avoid excessive degradation of the molecules or the formation of macro polymers in the plasma. The use of low pressure plasma is one method to achieve this. At low pressure the ions can not survive more than few milliseconds after the plasma is extinguished and at low pressure the dust particles grow relatively slow (about 10 s) to become of significant size. Pulsing the power is another standard way to diminish the plasma reactivity by decreasing the average energy transferred to the plasma per unit of time.
In general, in pulsed plasmas the standard method for suppression of dust formation is based on the fast decay of dust coagulation centres during the power off- time of the plasma. This can be regarded as a "natural death" of dust during the plasma off-time. At low pressure plasmas only a short period of power off-time is needed so that the power on- time can be relatively long (in the order of hundreds of ms). The duty cycle, defined as the power on time divided by the sum of the power on and power of time of these pulsing examples is large, typically in the range of 50-98 %. Pulsing the plasma with an off-time of a few milliseconds is enough to interrupt the growth of dust particles and to limit thus the dust formation.
Without being bound to theory the present invention is not based on the "natural dead" (decay) of dust coagulation centers but on minimizing their density in plasma so from the stage of Power on-time. To the contrary of standard method which is a manipulation of dust formation based on the decay of coagulation centers via adjustment of Power off-time this is rather a method based on preventing from the beginning the formation of the coagulation centers.
At atmospheric pressure high duty cycles could not be obtained until now. At atmospheric pressure duty cycles of less than 5% (for example 1%) were the maximum duty cycles achievable. Pulsing at atmospheric pressure is required to suppress dust formation but has the disadvantage of a slower treatment of a surface. So a low duty cycle is an option only for a limited range of gas mixtures provided that the density of reactive radicals reduces to almost 0 during plasma off-time. In the present invention we have now surprisingly found, that the duty cycle at atmospheric pressure can be increased significantly to values over 5% and even more than 10% for example 15% or 20%. As stated before in the treatment space 5 a combination of gases is introduced comprising a precursor an active gas for example oxygen and a combination of inert
gases. For most of the inert gas compositions a critical oxygen concentration can be identified below which the precursor will not decompose completely anymore, giving a deposition comprising the chemical compound or element to be deposited and the precursor or not completely decomposed precursor molecules. For the system hexamethyldisiloxane (HMDSO) as precursor, oxygen as the active gas and argon as the inert gas for example we found, that below the critical oxygen limit of 1.3% no complete decomposition of the HMDSO could be obtained.
To our surprise we found that addition of nitrogen to the gas mixture increases the efficiency of oxygen significantly which gives as big advantage that the dust formation is suppressed. The efficiency of deposition is increased when using nitrogen compared to the deposition without the use of nitrogen meaning that at the same active gas concentration the deposition is much more efficient and at higher active gas concentrations the formation of dust is suppressed. The use of very low amounts of oxygen gives, from a chemical point of view, homogeneous deposition and duty cycles can be obtained higher than 5% even higher than 10% for example 20%, 50%, 60%, 70%, 80 % or even 98% without or with only a very limited amount of dust formation. In one embodiment besides the precursor the gas composition comprises oxygen and nitrogen. Oxygen can be used for example from 0.01 to 25% of the gas composition and the gas composition can further comprise nitrogen in an amount from 99.99% to 1%. In addition to nitrogen the gas composition may comprise a noble gas like helium, neon or argon. The amount of the noble gas used can range from 1% to as high as 90 % of the total gas composition. Even a value of more than 95% for example 99% can be used. In this embodiment the total gas composition including the precursor amount would be oxygen in an amount ranging from 0.01 to 25% and noble gas nitrogen mixture ranging from 99.99% until 75 % with the amounts of nitrogen and noble gas as identified above. When using argon as noble gas, very good results have been obtained. Embodiments using only nitrogen as the inert gas besides the active gas can also advantageously be used.
Because of the fact, that pulsing reduces the formation of dust the power supply may be arranged to provide a periodic electrical signal with an on-time (ton) and an off- time (toff), the sum of the on-time and off-time being the period or cycle of the periodic electrical signal.
The power supply (being a part of the plasma control unit 11 as described with reference to Fig. 1) can be a power supply providing a wide range of frequencies. For example it can provide a low frequency (f= 10-450 kHz) electrical signal during the on- time. It can also provide a high frequency electrical signal for example f = 45OkHz - 30MHz. Also other frequencies can be provided like from 45OkHz-I MHz or from 1 to 20MHz and the like. The on-time may vary from very short, e.g. 20 ms, to short, e.g. 500 ms. Because of the beneficial effect of nitrogen also an on-time of more than 500ms can be used, for example Is. The on-time effectively results in a pulse train having a series of sine wave periods at the operating frequency, with a total duration of the on-time (e.g. 10 to 30 periods of a sine wave) of 0.1 to 0.3 ms. This is schematically shown in the graph of Fig. 2.
In another embodiment very short pulses are used in order to prevent the dust formation. Using these very short pulses, the dust formation is even further suppressed, while the deposition rate is kept at a high level because through the use of the gas compositions specified above a duty cycle of more than 10 % can be realised.
By using very short on-times of the APG plasma, further charging of the particles is effectively prevented, allowing to control the chemical reactions in the treatment space 5 even more efficiently.
In case of the use of very short pulses the power on- time of the APG plasma is short enough not to cause additional charging of the reactive species, thus allowing a much more effective deposition process.
Pulsing the plasma with an off-time in the order of milliseconds is enough to interrupt the growth of dust particles and to limit thus the dust formation. For minimizing the density of dust coagulation centers the use of an interval between pulses (Wf) in the order of the time of residence of the gas in the treatment space 5 of a reactor can also advantageously be used in the present invention. In this case the time between pulses should be comparable to the residence time of the gas in the discharge space. In the case of argon/oxygen/HMDSO for example there are reactive species with a longer lifetime which need to be flushed before the start of the next pulse. A residence time which is shorter than the cycle time (sum of pulse on-time and pulse off- time) is on the safe side, the residence time should in any case be chosen such, that there is no accumulation of dust coagulation centers. In case of the inventive embodiments using nitrogen, the residence time can be enlarged to values which are
higher than the cycle time. Residence times as high as 10 times the cycle times might be used in these embodiments.
The proposed pulsed plasma method is based on the suppression of formation of the dust coagulation centers from the initial phase during the power on-time ton. Furthermore, it is based on the decay of the dust coagulation centers by adjusting the power off-time (Wf) and by adjusting the gas composition. The total amount of coagulation centers seem to be determined by the amount of the precursor of the chemical compound or chemical element to be deposited in the plasma gas composition, and the gas mixture used, for example the percentage of oxygen and of course the gas flow as discussed above. In case the precursor amount in the gas mixture is reduced and/or the amount of reactive gas like oxygen, the amount of coagulation centers in the plasma gas will also be reduced. Reducing the precursor amount in the gas composition will off course influence the efficiency of the deposition process. Best results are obtained in general with a precursor concentration from 2 to 500 ppm of the gas composition and for example an oxygen concentration of e.g. 0.01% of the gas phase, or more, e.g. 2%, but less than 25% for example 10%.
In case of the inventive embodiments using nitrogen, an efficient way of controlling the generation of dust coagulation centers may be accomplished by having the power supply operate at a duty cycles in general from more than 1% or more than 5% for example 10%, 20%, 30%, 40%, 50%, 60% and even 98%, with short power on- times in the order of 0.05-0.5 ms. The power on-time (ton) and power off-time (Wf) can be adjusted in order to maintain a large density of reactive radicals and an efficient deposition process but within the limits imposed by the above mentioned conditions. Although oxygen as a reactive gas in this invention has a many advantages also other reactive gases might be used like for example hydrogen, carbon dioxide, ammonia, oxides of nitrogen, and the like.
In the present invention precursors can be can be selected from (but are not limited to): W(CO)6, Ni(CO)4, Mo(CO)O, Co2(CO)8, Rh4(CO)12, Re2(CO)10, Cr(CO)6, or Ru3(CO)12 , Tantalum Ethoxide (Ta(OC2H5)5), Tetra Dimethyl amino Titanium (or TDMAT) SiH4 CH4 , B2H6 or BC13 , WF6 , TiC14, GeH4,
Ge2H6Si2H6 (GeH3)3SiH ,(GeH3)2SiH2, hexamethyldisiloxane (HMDSO), tetramethyldisiloxane (TMDSO), 1,1,3,3,5,5-hexamethyltrisiloxane, hexamethylcyclotetrasiloxane, octamethylcyclotetrasiloxane,
decamethylcyclopentanesiloxane, tetraethoxysilane (TEOS), methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n- propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, i- butyltrimethoxysilane, n-hexyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, aminomethyltrimethylsilane, dimethyldimethylaminosilane, dimethylaminotrimethylsilane, allylaminotrimethylsilane, diethylaminodimethylsilane, 1-trimethylsilylpyrrole, 1- trimethylsilylpyrrolidine, isopropylaminomethyltrimethylsilane, diethylaminotrimethylsilane, anilinotrimethylsilane, 2-piperidinoethyltrimethylsilane, 3-butylaminopropyltrimethylsilane, 3-piperidinopropyltrimethylsilane, bis(dimethylamino)methylsilane, 1 -trimethylsilylimidazole, bis(ethylamino)dimethylsilane, bis(butylamino)dimethylsilane, 2- aminoethylaminomethyldimethylphenylsilane, 3-(4- methylpiperazinopropyl)trimethylsilane, dimethylphenylpiperazinomethylsilane, butyldimethyl-3-piperazinopropylsilane, dianilinodimethylsilane, bis(dimethylamino)diphenylsilane, 1 , 1 ,3,3-tetramethyldisilazane, 1,3- bis(chloromethyl)- 1 , 1 ,3,3-tetramethyldisilazane, hexamethyldisilazane, 1 ,3-divinyl- 1,1,3,3-tetramethyldisilazane, dibutyltin diacetate, aluminum isopropoxide, tris(2,4- pentadionato)aluminum, dibutyldiethoxytin, butyltin tris(2,4-pentanedionato), tetraethoxytin, methyltriethoxytin, diethyldiethoxytin, triisopropylethoxytin, ethylethoxytin, methylmethoxytin, isopropylisopropoxytin, tetrabutoxytin, diethoxytin, dimethoxytin, diisopropoxytin, dibutoxytin, dibutyryloxytin, diethyltin, tetrabutyltin, tin bis(2,4-pentanedionato), ethyltin acetoacetonato, ethoxytin (2,4-pentanedionato), dimethyltin (2,4-pentanedionato), diacetomethylacetatotin, diacetoxytin, dibutoxydiacetoxytin, diacetoxytin diacetoacetonato, tin hydride, tin dichloride, tin tetrachloride, triethoxytitanium, trimethoxytitanium, triisopropoxytitanium, tributoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, methyldimethoxytitanium, ethyltriethoxytitanium, methyltripropoxytitanium, triethyltitanium, triisopropyltitanium, tributyltitanium, tetraethyltitanium, tetraisopropyltitanium, tetrabutyltitanium, tetradimethylaminotitanium, dimethyltitanium di(2,4-pentanedionato), ethyltitanium tri(2,4-pentanedionato), titanium tris(2,4-pentanedionato), titanium tris(acetomethylacetato), triacetoxytitanium,
dipropoxypropionyloxytitanium, dibutyryloxytitanium,monotitanium hydride, dititanium hydride, trichlorotitanium, tetrachlorotitanium, tetraethylsilane, tetramethylsilane, tetraisopropylsilane, tetrabutylsilane, tetraisopropoxysilane, diethylsilane di(2,4-pentanedionato), methyltriethoxysilane, ethyltriethoxysilane, silane tetrahydride, disilane hexahydride, tetrachlorosilane, methyltrichlorosilane, diethyldichlorosilane, isopropoxyaluminum, tris(2,4-pentanedionato)nickel, bis(2,4- pentanedionato)manganese, isopropoxyboron, tri-n-butoxyantimony, tri-n- butylantimony, di-n-butylbis(2,4-pentanedionato)tin, di-n-butyldiacetoxytin, di-t- butyldiacetoxytin, tetraisopropoxytin, zinc di(2,4-pentanedionate), and combinations thereof. Furthermore precursors can be used as for example described in EP-A-
1351321 or EP-A- 1371752. Generally the precursors are used in a concentration of 2-500 ppm e.g. around 50 ppm of the total gas composition.
In another aspect of this invention the plasma gas including the precursor to be deposited via atmospheric pressure glow discharge plasma is brought into contact with two resin substrate 6a, 6b rolls synchronously via one device as can be seen in Fig. 1. This step will result in less consumption of precursor and/or carrier materials and as such to much more efficient application of plasma gas including precursor to be used onto the substrates 6a, 6b, which is from economical point and commercialization of view preferred. The figure is only illustrative for plasma gas contacting two rolls of resins synchronously, it may be understood that the method may include also the use of a remote plasma device and jetting the plasma gas including the precursor element to be deposited onto the 2 resin rolls synchronously. Further the use of atmospheric pressure glow discharge avoids the use of complex and expensive vacuum equipment which is preferred in order to make the process simpler and more cost-effective. Although the mechanism is not quite understood we believe that this improvement is related to far much better uniform and dense deposition of precursor element related to the use of our atmospheric pressure discharge.
As a result of the deposition on each substrate 6a, 6b an inorganic barrier 14 is formed with a thickness of 10 nm to lμm, preferably 20 nm to 300 nm and more preferably 50 nm to 200 nm.
Each inorganic barrier layer will display typically a water vapour transmission rate (WVTR) of about 0.03 g/m .day before the lamination step of this invention, which lamination step is described in more detail below using the embodiment of Fig. 3.
In Fig. 3 the lamination process is shown according an embodiment of this invention. The pair of inorganic barrier layers 6a', 6b' are suitably bonded or laminated together with an adhesive 15 on the inorganic barrier 14 side facing each other. In the embodiment shown in Fig. 3 this is accomplished by first forming two substrates 6a', 6b' with an inorganic barrier layer 14 in a single treatment space 5, similar to the embodiment of Fig. 1. The treated substrates 6a', 6b' are then fed to two laminating rollers 21, 22, and an adhesive material is applied the to inorganic layer side of substrates 6a', 6b' using an adhesive applicator 20. The laminating rollers 21, 22 are arranged to provide heat or radiation to the adhesive material between the treated substrates 6a', 6b', in order to cure or modify the adhesive material to form an adhesive layer 15.
As a result a multi layer stack structure 12 is obtained having an excellent barrier for water vapour. In one particular embodiment of this invention already excellent barrier properties were observed in the case when one [resin layer-inorganic] -layer stack combination 6a is adhered to another one [inorganic-organic]-layer stack combination 6b using an adhesive 15 between the two opposing face related inorganic barrier coatings 14 resulting in a multi layer stack structure 12 comprising the following layers as shown in cross section in Fig. 4a: i) organic resin (substrate 6a); ii) an inorganic barrier 14; iii) an adhesive 15; iv) an inorganic barrier 14 and v) an organic resin (substrate 6b). Also indicated are the semi-products 6a', 6b' each comprising a substrate 6a, 6b and a barrier layer 14.
In this particular embodiment the laminate structure may display a typical water vapour transmission rate (WVTR) of 7*10"4 g/m2.day.
It may be well understood that as a result of the 2-rolls-to-l-roll operation as described above in relation to Fig. 3, a further product multi-layer stack structure 12 can be prepared by using each produced multi- layer stack structure 12 as a starting substrate roll(s) in another separate 2 roll-to- 1 roll operation step. The separate structures 12 are laminated using an additional adhesive layer 16 as shown in the cross sectional view of Fig. 4b. As a result a thicker multi-stack layer structure may be prepared comprising i) [organic resin-inorganic barrier- adhesive- inorganic barrier- organic resin layer-adhesive]n layers and ii) [organic resin- inorganic barrier- adhesive- inorganic barrier-organic resin layer], layer where n is an integer larger than 0. As a
result even better barrier properties may be observed for these types of multi-stack layer structures.
Adhesives 15, 16 that may be applied for bonding the inorganic barrier layers 14 include all suitable thermoplastic-and elasto-plastic polymers; polymers which are curable by radiation such as by ultraviolet or electron-beam, by heat, by chemical initiators or by combinations thereof; organic or organic-containing adhesives, such as acrylics, urethanes, epoxides, polyolefins, organosilicones and others; and products of plasma-polymerization, oligomerization, or curing of organic-, organosilicon and other organometallic compounds, either volatile or deposited by other means such as spraying, sputtering, casting or dip-coating.
The adhesive forms an adhesive layer 15 bonding the two opposing faces of inorganic barrier layers 14 in the embodiment of Fig. 4a and an additional adhesive layer 16 bonding two substrates 6a, 6b of different multi-layer stack structures 12 in the embodiment of Fig. 4b. The adhesive layer 15, 16 may suitably have a thickness of 50 nm to 1000 μm, preferably from 100 nm to 100 μm.
The multi-layer stack structures 12 may be applied in several devices as under-or over-layer protection means. Preferred use of these multi-layers is in protecting OLEDs by using these multi-layers enveloping the OLED-devices.
The multi-layer material (single or multiple multi-layer stack structures 12) according to the invention may be used also in other types of devices, such as liquid crystal displays or in organic photovoltaic devices, which are known in prior art to require transparent materials impermeable to oxygen and water vapour.
EXAMPLES As a substrate material 6a, 6b optical grade PEN was used having a thickness of
90 micron. WVTR of the PEN substrate without coating was quantified by Mocon Aquatran and is typically 0.27+/-0.03 g/m2.day .
Comparitive example Typically 100 nm thick inorganic layers were deposited on optical grade PEN sheets using a low vacuum ICP plasma enhanced CVD process using argon, HMDSO and oxygen.
The layer thickness of 100 nm SiO2 was quantified by Spectroscopic Ellipsometry (Woollam M-2000) and the WVTR was quantified by Mocon Aquatran. The WVTR of the barrier samples was typically 0.1g/m2.day (at 2OC and 60%RH). Subsequently two barrier films were laminated face to face (barrier to barrier) using a test-laminator with a UV curable hydrophobic acrylate and UV-cured. The acrylate layer has a thickness of typically 10 micron.
Consequently, the WVTR is measured of the laminate structure using the Mocon Aquatran. The WVTR obtained is typically 0.01 g/m2.day.
Example 1
Two barrier films 14 of 50 nm thick are deposited synchronously using the electrode set-up as shown in Fig. 1 using an atmospheric pressure plasma device 10. On both sides of the substrates 6a, 6b facing the plasma discharge a SiOx layer 14 is deposited. Directly, after depositing the inorganic layer 14 the two substrates 6a', 6b' are brought together and laminated with the same hydrophobic acrylate as above with a thickness of 10 micron followed by UV-curing. Under the same conditions more barrier samples are produced and part of this material is prepared for permeability characterization by Mocon.
The WVTR of the individual layers 6a', 6b' is typically 0.03 g/m2.day, whereas the permeability of the laminate structure 12 is typically less than 1*10~3 g/m2.day.
Example 2
Two barrier films 14 of 100 nm thick are deposited in one time using the electrode set-up as shown in Fig. 1. On both sides of the substrates 6a, 6b facing the plasma discharge a SiOx layer 14 is deposited. Directly, after depositing the inorganic layer 14 the two substrates 6a', 6b' are brought together and laminated using the same thickness and same acrylate layer 15.
Under same conditions more barrier samples are produced, part of this material is sampled for permeability characterization by Mocon. WVTR of the individual layers 6a', 6b' is typically 0.03 g/m2.day, whereas the permeability of the laminate structure 12 is below the detection limit of the Mocon
Aquatran.
Subsequently, the permeability is characterized by the calcium corrosion test. This method allows characterization of the average WVTR as low as 10~5 to 10~6 g/m2.day at 4O0C / 90%RH. The WVTR for the multi-layer stack structure 12 was found to be typically in the order of 10~4 g/m2.day. Moreover the method can be used too to evaluate defect resolved calcium corrosion. By repeatedly measuring the development of the defects it was observed by optical microscopy that very small defects tend to appear after more than 500 hours. However, defects remain very small, i.e. there is no growth of the defects and as a matter of fact defects remain so small that they are not visible by naked eye.
Claims
1 A method for manufacturing a multi-layer stack structure (12), the structure (12) comprising in order: a substrate (6a) - a barrier layer (14) - an adhesive layer (15) - a barrier layer (14) - a substrate (6b), the method comprising: a) providing two substrates (6a, 6b) in a single treatment space (5), the treatment space (5) being formed between at least two electrodes (2, 3) for generating an atmospheric pressure glow discharge plasma in the single treatment space (5); b) treating the facing surfaces of the two substrates (6a, 6b) simultaneously in the single treatment space (5); c) laminating the two treated substrates (6a', 6b') with an adhesive layer (15) in between the facing surfaces to obtain the multi-layer stack structure (12).
2. The method according to claim 1, further comprising laminating two or more multi-layer stack structures (12) with an additional adhesive layer (16) in between.
3. The method according to claim 1 or 2, in which the substrates (6a, 6b) are provided as sheets to obtain the multi-layer stack structure (12) in a continuous process.
4. The method according to any one of claims 1-3, in which the substrates (6a, 6b) are organic resin films.
5. The method according to any one of claims 1-4, in which treating the facing surfaces comprises depositing an inorganic material on the substrate surface to form the barrier layer (14).
6. Method according to any one of claims 1-5, in which treating the facing surfaces is executed with a duty cycle above 10%, preferably above 60%.
7. The method according to any one of claims 1-6, in which an atmospheric pressure glow discharge is generated by applying electrical power from a power supply (11) to the at least two electrodes (2, 3) in the treatment space (5) during an on-time (ton), the treatment space (5) being filled with a gas composition, including a precursor of the chemical compound or element to be deposited, wherein the gas composition comprises an amount of nitrogen between 1 and 99.99% and an amount of oxygen between 0.01 and 25%.
8. An OLED device comprising a multi-layer structure (12) obtained according to the method according to any one of claims 1-7.
9. A device comprising a multi-layer structure (12) obtained according to the method according to any one of claims 1-7.
10. An apparatus for producing a multi-layer stack structure, the apparatus comprising a treatment space (5) with at least two electrodes (2, 3) connected to a plasma control unit (11) for generating an atmospheric pressure glow discharge plasma in the treatment space (5), and a gas supply device (8) in communication with the single treatment space (5) for providing compounds in the treatment space (5), in which the treatment space (5) is a single treatment space (5) formed between the at least two electrodes (2, 3), and the apparatus further comprising a feeder system (4) for providing two substrates (6a, 6b) simultaneously in the single treatment space (5) for treatment using the generated atmospheric pressure glow discharge plasma, and a laminating system (20, 21) for laminating the two treated substrates (6a', 6b') with an adhesive layer (15) in between.
11. Apparatus according to claim 10, in which the feeder system comprises rolls (4), and the at least two electrodes (2, 3) comprise cylinder type electrodes.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/866,704 US8445897B2 (en) | 2008-02-08 | 2009-01-22 | Method for manufacturing a multi-layer stack structure with improved WVTR barrier property |
AT09708722T ATE523067T1 (en) | 2008-02-08 | 2009-01-22 | METHOD FOR PRODUCING A MULTI-LAYER STACK STRUCTURE WITH IMPROVED WVTR BOUNDARY PROPERTY |
JP2010545817A JP5473946B2 (en) | 2008-02-08 | 2009-01-22 | Method for manufacturing multilayer stack structure with improved WVTR barrier property |
EP09708722A EP2241165B1 (en) | 2008-02-08 | 2009-01-22 | Method for manufacturing a multi_layer stack structure with improved wvtr barrier property |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08151215 | 2008-02-08 | ||
EP08151215.4 | 2008-02-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009099325A1 true WO2009099325A1 (en) | 2009-08-13 |
Family
ID=39575531
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NL2009/050027 WO2009099325A1 (en) | 2008-02-08 | 2009-01-22 | Method for manufacturing a multi_layer stack structure with improved wvtr barrier property |
Country Status (5)
Country | Link |
---|---|
US (1) | US8445897B2 (en) |
EP (1) | EP2241165B1 (en) |
JP (1) | JP5473946B2 (en) |
AT (1) | ATE523067T1 (en) |
WO (1) | WO2009099325A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012010867A1 (en) * | 2010-07-21 | 2012-01-26 | Fujifilm Manufacturing Europe Bv | Method for manufacturing a barrier coating |
WO2012010866A1 (en) | 2010-07-21 | 2012-01-26 | Fujifilm Manufacturing Europe Bv | Method for manufacturing a barrier layer |
US8323753B2 (en) | 2006-05-30 | 2012-12-04 | Fujifilm Manufacturing Europe B.V. | Method for deposition using pulsed atmospheric pressure glow discharge |
US8338307B2 (en) | 2007-02-13 | 2012-12-25 | Fujifilm Manufacturing Europe B.V. | Substrate plasma treatment using magnetic mask device |
US8702999B2 (en) | 2008-02-01 | 2014-04-22 | Fujifilm Manufacturing Europe B.V. | Method and apparatus for plasma surface treatment of a moving substrate |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007024134A1 (en) * | 2005-08-26 | 2007-03-01 | Fujifilm Manufacturing Europe B.V. | Method and arrangement for generating and controlling a discharge plasma |
US20090324971A1 (en) * | 2006-06-16 | 2009-12-31 | Fujifilm Manufacturing Europe B.V. | Method and apparatus for atomic layer deposition using an atmospheric pressure glow discharge plasma |
US8648932B2 (en) | 2009-08-13 | 2014-02-11 | Olive Medical Corporation | System, apparatus and methods for providing a single use imaging device for sterile environments |
TWI501441B (en) * | 2012-08-24 | 2015-09-21 | Ind Tech Res Inst | Discontinuous compound barrier layer, method for forming the same and package using the same |
KR101970569B1 (en) * | 2012-12-17 | 2019-04-19 | 엘지디스플레이 주식회사 | Organic light emitting diode display device |
TW201445794A (en) * | 2013-05-27 | 2014-12-01 | Wistron Corp | Package structure of organic optic-electro device and method for packaging thereof |
KR101563341B1 (en) * | 2014-04-29 | 2015-11-06 | 한국과학기술원 | Vapor deposition apparatus |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999004411A1 (en) * | 1997-07-14 | 1999-01-28 | The University Of Tennessee Research Corporation | Plasma treater systems and treatment methods |
US6413645B1 (en) * | 2000-04-20 | 2002-07-02 | Battelle Memorial Institute | Ultrabarrier substrates |
WO2007089146A1 (en) * | 2006-02-02 | 2007-08-09 | Fujifilm Manufacturing Europe B.V. | Method for surface treatment by plasma and surface treatment apparatus |
US7298072B2 (en) * | 2001-07-06 | 2007-11-20 | Nova-Plasma Inc. | Transparent support for organic light emitting device |
WO2007139379A1 (en) * | 2006-05-30 | 2007-12-06 | Fujifilm Manufacturing Europe B.V. | Method and apparatus for deposition using pulsed atmospheric pressure glow discharge |
Family Cites Families (61)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3224234A1 (en) * | 1981-09-01 | 1983-03-10 | Siemens AG, 1000 Berlin und 8000 München | METHOD FOR PRODUCING METAL-FREE STRIPS IN THE METAL STEAMING OF AN INSULATING TAPE AND DEVICE FOR IMPLEMENTING THE METHOD |
JPS58111380A (en) | 1981-12-24 | 1983-07-02 | Seiko Epson Corp | Manufacture of amorphous silicon solar cell |
JPS58217344A (en) | 1983-06-01 | 1983-12-17 | 旭化成ポリフレックス株式会社 | Barriering plastic laminated sheet |
US4681780A (en) * | 1983-12-01 | 1987-07-21 | Polaroid Corporation | Continuously cleaned rotary coating mask |
US4631199A (en) * | 1985-07-22 | 1986-12-23 | Hughes Aircraft Company | Photochemical vapor deposition process for depositing oxide layers |
JPS6433932A (en) | 1987-07-29 | 1989-02-03 | Matsushita Electric Ind Co Ltd | Etching apparatus |
JPH0494169A (en) | 1990-08-09 | 1992-03-26 | Kanegafuchi Chem Ind Co Ltd | Thin film diode element |
US5187457A (en) * | 1991-09-12 | 1993-02-16 | Eni Div. Of Astec America, Inc. | Harmonic and subharmonic filter |
FR2704558B1 (en) * | 1993-04-29 | 1995-06-23 | Air Liquide | METHOD AND DEVICE FOR CREATING A DEPOSIT OF SILICON OXIDE ON A SOLID TRAVELING SUBSTRATE. |
JP3148910B2 (en) | 1993-09-01 | 2001-03-26 | 日本真空技術株式会社 | Plasma CVD film forming method |
US6342277B1 (en) * | 1996-08-16 | 2002-01-29 | Licensee For Microelectronics: Asm America, Inc. | Sequential chemical vapor deposition |
JP3904523B2 (en) * | 1997-04-17 | 2007-04-11 | 株式会社クレハ | ELECTROLUMINESCENT DEVICE AND MANUFACTURING METHOD THEREOF |
DE19728472A1 (en) | 1997-07-03 | 1999-01-07 | Siemens Ag | Structuring process |
JP2000026632A (en) | 1998-07-13 | 2000-01-25 | Sekisui Chem Co Ltd | Thin film formation on film substrate using normal pressure plasma |
JP2000212753A (en) * | 1999-01-22 | 2000-08-02 | Sekisui Chem Co Ltd | Manufacture of surface treated article |
US6774018B2 (en) | 1999-02-01 | 2004-08-10 | Sigma Laboratories Of Arizona, Inc. | Barrier coatings produced by atmospheric glow discharge |
EP1029702B1 (en) | 1999-02-15 | 2004-04-14 | Konica Corporation | Surface treatment method, production method for ink jet recording medium, and ink jet recording medium |
JP2000313962A (en) | 1999-04-26 | 2000-11-14 | Sekisui Chem Co Ltd | DEPOSITION OF TiO2 THIN FILM USING DISCHARGE PLASMA |
US6391785B1 (en) | 1999-08-24 | 2002-05-21 | Interuniversitair Microelektronica Centrum (Imec) | Method for bottomless deposition of barrier layers in integrated circuit metallization schemes |
TW520453B (en) * | 1999-12-27 | 2003-02-11 | Seiko Epson Corp | A method to fabricate thin insulating films |
DE10011276A1 (en) * | 2000-03-08 | 2001-09-13 | Wolff Walsrode Ag | Process employing indirect atmospheric plasmatron, surface-treats or coats thin metallic foil or polymer sheet |
EP1264330B1 (en) | 2000-03-14 | 2003-07-16 | Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. | Method and device for the plasma-activated surface treatment and use of the inventive method |
US6524431B1 (en) * | 2000-11-10 | 2003-02-25 | Helix Technology Inc. | Apparatus for automatically cleaning mask |
TW531801B (en) | 2000-11-14 | 2003-05-11 | Sekisui Chemical Co Ltd | Normal plasma processing method and processing device |
EP2233606B1 (en) * | 2000-12-12 | 2013-02-13 | Konica Corporation | Plasma discharge apparatus |
US6464779B1 (en) * | 2001-01-19 | 2002-10-15 | Novellus Systems, Inc. | Copper atomic layer chemical vapor desposition |
GB0113751D0 (en) * | 2001-06-06 | 2001-07-25 | Dow Corning | Surface treatment |
US6861334B2 (en) * | 2001-06-21 | 2005-03-01 | Asm International, N.V. | Method of fabricating trench isolation structures for integrated circuits using atomic layer deposition |
US7098131B2 (en) * | 2001-07-19 | 2006-08-29 | Samsung Electronics Co., Ltd. | Methods for forming atomic layers and thin films including tantalum nitride and devices including the same |
JP2003049273A (en) * | 2001-08-08 | 2003-02-21 | Kobe Steel Ltd | Plasma cvd device and film deposition method by plasma cvd |
US6756318B2 (en) * | 2001-09-10 | 2004-06-29 | Tegal Corporation | Nanolayer thick film processing system and method |
JP2003154255A (en) * | 2001-11-21 | 2003-05-27 | Okura Ind Co Ltd | Method and apparatus for surface-treatment of sheet like base material with atmospheric discharge plasma |
DE10161469A1 (en) * | 2001-12-13 | 2003-07-03 | Schott Glas | Volume-optimized reactor for simultaneous coating of spectacle lenses on both sides |
JP3859518B2 (en) | 2002-01-15 | 2006-12-20 | 住友ベークライト株式会社 | Transparent water vapor barrier film |
EP1351321B1 (en) | 2002-04-01 | 2013-12-25 | Konica Corporation | Support and organic electroluminescence element comprising the support |
TWI273143B (en) | 2002-06-10 | 2007-02-11 | Konica Corp | Layer formation method, and substrate with a layer formed by the method |
US6774569B2 (en) * | 2002-07-11 | 2004-08-10 | Fuji Photo Film B.V. | Apparatus for producing and sustaining a glow discharge plasma under atmospheric conditions |
US7288204B2 (en) | 2002-07-19 | 2007-10-30 | Fuji Photo Film B.V. | Method and arrangement for treating a substrate with an atmospheric pressure glow plasma (APG) |
US20050084610A1 (en) * | 2002-08-13 | 2005-04-21 | Selitser Simon I. | Atmospheric pressure molecular layer CVD |
EP1403902A1 (en) | 2002-09-30 | 2004-03-31 | Fuji Photo Film B.V. | Method and arrangement for generating an atmospheric pressure glow discharge plasma (APG) |
BRPI0413769A (en) | 2003-09-09 | 2006-10-31 | Dow Global Technologies Inc | process for depositing a film coating on the exposed surface of a substrate |
GB0323295D0 (en) | 2003-10-04 | 2003-11-05 | Dow Corning | Deposition of thin films |
US20050079418A1 (en) * | 2003-10-14 | 2005-04-14 | 3M Innovative Properties Company | In-line deposition processes for thin film battery fabrication |
EP1626613B8 (en) | 2004-08-13 | 2007-03-07 | Fuji Film Manufacturing Europe B.V. | Method and arrangement for controlling a glow discharge plasma under atmospheric conditions |
JP4668208B2 (en) | 2003-12-22 | 2011-04-13 | フジフィルム マニュファクチャリング ユーロプ ビー.ブイ. | Method and apparatus for removing dirt from substrate surface using atmospheric pressure glow plasma |
EP1548795A1 (en) | 2003-12-22 | 2005-06-29 | Fuji Photo Film B.V. | Method and apparatus for stabilizing a glow discharge plasma under atmospheric conditions |
JP2006004740A (en) | 2004-06-17 | 2006-01-05 | Seiko Epson Corp | Film-forming method, manufacturing method of display device, display device, and electronic equipment |
DE102004043384B4 (en) | 2004-09-08 | 2010-06-17 | Schott Ag | Process for producing a coated hollow body substrate of at least polyethylene terephthalate |
JP2006201538A (en) * | 2005-01-21 | 2006-08-03 | Seiko Epson Corp | Mask, manufacturing method of the mask, pattern forming method and wiring pattern forming method |
US20060231908A1 (en) * | 2005-04-13 | 2006-10-19 | Xerox Corporation | Multilayer gate dielectric |
JP2009503781A (en) | 2005-07-26 | 2009-01-29 | ピーエスエム インコーポレイティド | Injection type plasma processing apparatus and method |
KR101218114B1 (en) | 2005-08-04 | 2013-01-18 | 주성엔지니어링(주) | Etching apparatus using the plasma |
WO2007024134A1 (en) | 2005-08-26 | 2007-03-01 | Fujifilm Manufacturing Europe B.V. | Method and arrangement for generating and controlling a discharge plasma |
US7763114B2 (en) | 2005-12-28 | 2010-07-27 | 3M Innovative Properties Company | Rotatable aperture mask assembly and deposition system |
JP2009526129A (en) * | 2006-02-09 | 2009-07-16 | フジフィルム マニュファクチャリング ユーロプ ビー.ブイ. | Short pulse atmospheric pressure glow discharge method and apparatus |
US20090324971A1 (en) * | 2006-06-16 | 2009-12-31 | Fujifilm Manufacturing Europe B.V. | Method and apparatus for atomic layer deposition using an atmospheric pressure glow discharge plasma |
EP2109876B1 (en) * | 2007-02-13 | 2015-05-06 | Fuji Film Manufacturing Europe B.V. | Substrate plasma treatment using magnetic mask device |
WO2009096785A1 (en) | 2008-02-01 | 2009-08-06 | Fujifilm Manufacturing Europe B.V. | Method and apparatus for plasma surface treatment of a moving substrate |
EP2528082A3 (en) * | 2008-02-21 | 2014-11-05 | FUJIFILM Manufacturing Europe B.V. | Plasma treatment apparatus with an atmospheric pressure glow discharge electrode configuration |
WO2009148305A1 (en) * | 2008-06-06 | 2009-12-10 | Fujifilm Manufacturing Europe B.V. | Method and apparatus for plasma surface treatment of moving substrate |
JP2012517530A (en) | 2009-02-12 | 2012-08-02 | フジフィルム・マニュファクチュアリング・ヨーロッパ・ベスローテン・フエンノートシャップ | Two-layer barrier on polymer substrate |
-
2009
- 2009-01-22 EP EP09708722A patent/EP2241165B1/en not_active Not-in-force
- 2009-01-22 AT AT09708722T patent/ATE523067T1/en not_active IP Right Cessation
- 2009-01-22 US US12/866,704 patent/US8445897B2/en not_active Expired - Fee Related
- 2009-01-22 JP JP2010545817A patent/JP5473946B2/en not_active Expired - Fee Related
- 2009-01-22 WO PCT/NL2009/050027 patent/WO2009099325A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999004411A1 (en) * | 1997-07-14 | 1999-01-28 | The University Of Tennessee Research Corporation | Plasma treater systems and treatment methods |
US6413645B1 (en) * | 2000-04-20 | 2002-07-02 | Battelle Memorial Institute | Ultrabarrier substrates |
US7298072B2 (en) * | 2001-07-06 | 2007-11-20 | Nova-Plasma Inc. | Transparent support for organic light emitting device |
WO2007089146A1 (en) * | 2006-02-02 | 2007-08-09 | Fujifilm Manufacturing Europe B.V. | Method for surface treatment by plasma and surface treatment apparatus |
WO2007139379A1 (en) * | 2006-05-30 | 2007-12-06 | Fujifilm Manufacturing Europe B.V. | Method and apparatus for deposition using pulsed atmospheric pressure glow discharge |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8323753B2 (en) | 2006-05-30 | 2012-12-04 | Fujifilm Manufacturing Europe B.V. | Method for deposition using pulsed atmospheric pressure glow discharge |
US8338307B2 (en) | 2007-02-13 | 2012-12-25 | Fujifilm Manufacturing Europe B.V. | Substrate plasma treatment using magnetic mask device |
US8702999B2 (en) | 2008-02-01 | 2014-04-22 | Fujifilm Manufacturing Europe B.V. | Method and apparatus for plasma surface treatment of a moving substrate |
WO2012010867A1 (en) * | 2010-07-21 | 2012-01-26 | Fujifilm Manufacturing Europe Bv | Method for manufacturing a barrier coating |
WO2012010866A1 (en) | 2010-07-21 | 2012-01-26 | Fujifilm Manufacturing Europe Bv | Method for manufacturing a barrier layer |
US20130122719A1 (en) * | 2010-07-21 | 2013-05-16 | Fujifilm Manufacturing Europe B.V. | Method for Manufacturing a Barrier on a Sheet and a Sheet for PV Modules |
US20130178060A1 (en) * | 2010-07-21 | 2013-07-11 | Fujifilm Manufacturing Europe B.V. | Method for Manufacturing a Barrier Layer on a Substrate and a Multi-Layer Stack |
US8815749B2 (en) * | 2010-07-21 | 2014-08-26 | Fujifilm Manufacturing Europe B.V. | Method for manufacturing a barrier layer on a substrate and a multi-layer stack |
US8815750B2 (en) * | 2010-07-21 | 2014-08-26 | Fujifilm Manufacturing Europe B.V. | Method for manufacturing a barrier on a sheet and a sheet for PV modules |
Also Published As
Publication number | Publication date |
---|---|
JP5473946B2 (en) | 2014-04-16 |
JP2011514265A (en) | 2011-05-06 |
EP2241165A1 (en) | 2010-10-20 |
ATE523067T1 (en) | 2011-09-15 |
EP2241165B1 (en) | 2011-08-31 |
US20110049491A1 (en) | 2011-03-03 |
US8445897B2 (en) | 2013-05-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2241165B1 (en) | Method for manufacturing a multi_layer stack structure with improved wvtr barrier property | |
JP5725865B2 (en) | Plasma processing apparatus and method for processing a substrate using an atmospheric pressure glow discharge electrode configuration | |
US9891473B2 (en) | Laminated film, organic electroluminescence device, photoelectric converter, and liquid crystal display | |
JP2016164303A (en) | Apparatus for depositing high-performance coatings | |
WO2014123201A1 (en) | Gas barrier film and method for manufacturing same | |
US20110311734A1 (en) | Two Layer Barrier on Polymeric Substrate | |
EP2596148B1 (en) | Method for manufacturing a barrier coating. | |
EP2226832A1 (en) | Substrate plasma treatment using side tabs | |
WO2008147184A2 (en) | Atmospheric pressure glow discharge plasma method and system using heated substrate | |
US9763345B2 (en) | Gas barrier laminated body, method for producing same, member for electronic device, and electronic device | |
EP2596147B1 (en) | Method for manufacturing a barrier layer | |
TWI666121B (en) | Laminated film, organic electroluminescence device, photoelectric conversion device, and liquid crystal display | |
US20150017339A1 (en) | Substrate Structure Grown By Plasma Deposition | |
JP5719106B2 (en) | Transparent gas barrier film and method for producing transparent gas barrier film | |
KR102193005B1 (en) | Gas barrier layer, gas barrier film, organic electroluminescence element and electronic paper, and method for producing of gas barrier film | |
JPWO2014109250A1 (en) | Functional film production method, functional film production apparatus, and organic electroluminescence device comprising functional film |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09708722 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009708722 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010545817 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12866704 Country of ref document: US |