EP1877462A1 - Semiconductors containing perfluoroether acyl oligothiophene compounds - Google Patents
Semiconductors containing perfluoroether acyl oligothiophene compoundsInfo
- Publication number
- EP1877462A1 EP1877462A1 EP06735988A EP06735988A EP1877462A1 EP 1877462 A1 EP1877462 A1 EP 1877462A1 EP 06735988 A EP06735988 A EP 06735988A EP 06735988 A EP06735988 A EP 06735988A EP 1877462 A1 EP1877462 A1 EP 1877462A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- formula
- semiconductor layer
- layer
- compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 146
- 150000001875 compounds Chemical class 0.000 title claims abstract description 70
- 229920001774 Perfluoroether Polymers 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 57
- 238000000151 deposition Methods 0.000 claims abstract description 19
- 239000010410 layer Substances 0.000 claims description 154
- -1 alkyl lithium compound Chemical class 0.000 claims description 58
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 43
- 239000010409 thin film Substances 0.000 claims description 29
- 239000002335 surface treatment layer Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 20
- 229930192474 thiophene Natural products 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical group FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 13
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical group FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 239000010702 perfluoropolyether Substances 0.000 claims description 5
- 239000011968 lewis acid catalyst Substances 0.000 claims description 4
- 125000006551 perfluoro alkylene group Chemical group 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims 2
- 238000010791 quenching Methods 0.000 claims 2
- 230000000171 quenching effect Effects 0.000 claims 2
- 125000002252 acyl group Chemical group 0.000 abstract description 11
- 239000000463 material Substances 0.000 description 45
- 239000000047 product Substances 0.000 description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 239000000758 substrate Substances 0.000 description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 238000004293 19F NMR spectroscopy Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 239000003989 dielectric material Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000012267 brine Substances 0.000 description 8
- 230000037230 mobility Effects 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- 150000003577 thiophenes Chemical class 0.000 description 8
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 5
- 238000000206 photolithography Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000006619 Stille reaction Methods 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 238000003491 array Methods 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000006384 oligomerization reaction Methods 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KBVDUUXRXJTAJC-UHFFFAOYSA-N 2,5-dibromothiophene Chemical compound BrC1=CC=C(Br)S1 KBVDUUXRXJTAJC-UHFFFAOYSA-N 0.000 description 3
- SYNPRNNJJLRHTI-UHFFFAOYSA-N 2-(hydroxymethyl)butane-1,4-diol Chemical compound OCCC(CO)CO SYNPRNNJJLRHTI-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000003855 acyl compounds Chemical class 0.000 description 3
- 230000010933 acylation Effects 0.000 description 3
- 238000005917 acylation reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002800 charge carrier Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 125000006344 nonafluoro n-butyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 3
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 3
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000013545 self-assembled monolayer Substances 0.000 description 3
- 238000000859 sublimation Methods 0.000 description 3
- 230000008022 sublimation Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- DUIIPHYNGUDOIM-UHFFFAOYSA-N 2-(4-ethenylphenyl)acetonitrile Chemical compound C=CC1=CC=C(CC#N)C=C1 DUIIPHYNGUDOIM-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000005529 alkyleneoxy group Chemical group 0.000 description 2
- 238000000065 atmospheric pressure chemical ionisation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 150000001793 charged compounds Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000000572 ellipsometry Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000000155 isotopic effect Effects 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- BDMCJNPMLSZYSL-UHFFFAOYSA-N methyl 2-[2-(2-methoxyethoxy)ethoxy]acetate Chemical compound COCCOCCOCC(=O)OC BDMCJNPMLSZYSL-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000002094 self assembled monolayer Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VFBFMXNJIXKWFO-NUHJPDEHSA-N (2R)-1-[4,5-difluoro-2-(3,4,5-trifluorothiophen-2-yl)thiophen-3-yl]-2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]propan-1-one Chemical compound FC=1C(=C(SC=1F)C=1SC(=C(C=1F)F)F)C([C@](OC(C(OC(C(C(F)(F)F)(F)F)(F)F)(C(F)(F)F)F)(F)F)(C(F)(F)F)F)=O VFBFMXNJIXKWFO-NUHJPDEHSA-N 0.000 description 1
- IJAOUFAMBRPHSJ-UHFFFAOYSA-N (4-ethenylphenyl)methylphosphonic acid Chemical compound OP(O)(=O)CC1=CC=C(C=C)C=C1 IJAOUFAMBRPHSJ-UHFFFAOYSA-N 0.000 description 1
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- KXSFECAJUBPPFE-UHFFFAOYSA-N 2,2':5',2''-terthiophene Chemical compound C1=CSC(C=2SC(=CC=2)C=2SC=CC=2)=C1 KXSFECAJUBPPFE-UHFFFAOYSA-N 0.000 description 1
- STRDVASOPHTUSR-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methyl]-2-methylpropanedinitrile Chemical compound N#CC(C#N)(C)CC1=CC=C(C=C)C=C1 STRDVASOPHTUSR-UHFFFAOYSA-N 0.000 description 1
- QCROIGXMIMERQO-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methyl]prop-2-enoic acid Chemical compound OC(=O)C(=C)CC1=CC=C(C=C)C=C1 QCROIGXMIMERQO-UHFFFAOYSA-N 0.000 description 1
- VRBFTYUMFJWSJY-UHFFFAOYSA-N 28804-46-8 Chemical compound ClC1CC(C=C2)=CC=C2C(Cl)CC2=CC=C1C=C2 VRBFTYUMFJWSJY-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- RUPGPUIMWGBLBL-UHFFFAOYSA-N 3-[2-cyanoethyl-[2-(4-ethenylphenyl)ethyl]amino]propanenitrile Chemical compound C=CC1=CC=C(CCN(CCC#N)CCC#N)C=C1 RUPGPUIMWGBLBL-UHFFFAOYSA-N 0.000 description 1
- XCMISAPCWHTVNG-UHFFFAOYSA-N 3-bromothiophene Chemical compound BrC=1C=CSC=1 XCMISAPCWHTVNG-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- QPIBHIXKUQKNFP-UHFFFAOYSA-N 4-chloro-3-fluorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C(F)=C1 QPIBHIXKUQKNFP-UHFFFAOYSA-N 0.000 description 1
- JPWDZWWURNTQQE-UHFFFAOYSA-N 5-cyano-3-(2-cyanoethyl)pent-2-enamide Chemical compound C(#N)CCC(=CC(=O)N)CCC#N JPWDZWWURNTQQE-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
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- QNQUGVRZXXLFMM-UHFFFAOYSA-N S1C([Li])=CC=C1C1=CC=CS1 Chemical compound S1C([Li])=CC=C1C1=CC=CS1 QNQUGVRZXXLFMM-UHFFFAOYSA-N 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- XBDYBAVJXHJMNQ-UHFFFAOYSA-N Tetrahydroanthracene Natural products C1=CC=C2C=C(CCCC3)C3=CC2=C1 XBDYBAVJXHJMNQ-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 description 1
- JGTAEKZVTPPMGA-UHFFFAOYSA-N [Li]C1=CC=C(Br)S1 Chemical compound [Li]C1=CC=C(Br)S1 JGTAEKZVTPPMGA-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 150000001265 acyl fluorides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 229910021523 barium zirconate Inorganic materials 0.000 description 1
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 description 1
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000009838 combustion analysis Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 1
- NDJGRZWOYSPXCB-UHFFFAOYSA-N fluoro hypofluorite;thiophene Chemical class FOF.C=1C=CSC=1 NDJGRZWOYSPXCB-UHFFFAOYSA-N 0.000 description 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical class [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000006341 heptafluoro n-propyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- JDPSFRXPDJVJMV-UHFFFAOYSA-N hexadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCP(O)(O)=O JDPSFRXPDJVJMV-UHFFFAOYSA-N 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- GJWAEWLHSDGBGG-UHFFFAOYSA-N hexylphosphonic acid Chemical compound CCCCCCP(O)(O)=O GJWAEWLHSDGBGG-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- AQHOENYROFTJJB-UHFFFAOYSA-M magnesium;5-bromo-2h-thiophen-2-ide;bromide Chemical compound [Mg+2].[Br-].BrC1=CC=[C-]S1 AQHOENYROFTJJB-UHFFFAOYSA-M 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- QDVIBEPABUQWMB-UHFFFAOYSA-N methyl 2-(2-butoxyethoxy)acetate Chemical compound CCCCOCCOCC(=O)OC QDVIBEPABUQWMB-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000813 microcontact printing Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000679 poly(dimethylsiloxane-co-methylphenylsiloxane) Polymers 0.000 description 1
- 229920003251 poly(α-methylstyrene) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229920006249 styrenic copolymer Polymers 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 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
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- GCYLHKHGKQNXHN-UHFFFAOYSA-N thiophen-2-yltin Chemical compound [Sn]C1=CC=CS1 GCYLHKHGKQNXHN-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/28—Halogen atoms
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K99/00—Subject matter not provided for in other groups of this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/468—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
- H10K10/474—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising a multilayered structure
Definitions
- the present invention provides semiconductor devices and methods of making semiconductor devices that include a semiconductor layer that contains a perfluoroether acyl oligothiophene compound.
- inorganic materials have dominated the semiconductor industry.
- silicon arsenide and gallium arsenide have been used as semiconductor materials
- silicon dioxide has been used as an insulator material
- metals such as aluminum and copper have been used as electrode materials.
- organic materials may enable lower cost manufacturing of electronic devices, may enable large area applications, and may enable the use of flexible circuit supports for display backplanes or integrated circuits.
- organic semiconductor materials have been considered, the most common being fused aromatic ring compounds as exemplified by tetracene and pentacene, bis(acenyl)acetylene, and acene-thiophenes; oligomeric materials containing thiophene or fluorene units; and polymeric materials such as regioregular poly(3-alkylthiophene). At least some of these organic semiconductor materials have performance characteristics such as charge-carrier mobility, on/off current ratios, and sub-threshold voltages that are comparable or superior to those of amorphous silicon-based devices.
- ⁇ , ⁇ '-conjugated thiophene oligomers (nTs) and polymers (polythiophenes-PTs) have attracted great interest as semiconducting elements in organic thin-film transistors (TFTs).
- TFTs organic thin-film transistors
- the organic material must support a channel of holes or electrons (p- or n-type semiconductor, respectively) created by the gate electrode bias, which switches the device "on".
- the charge mobility of the material must be sufficiently large to increase the source-drain on-conduction by many orders of magnitude over the "off state.
- the density of the charge carrier in the channel is modulated by voltage applied at the gate electrode
- U.S. 6,585,914 (Marks et al.) describe ⁇ , ⁇ -diperfluoroalkylsexithiophene- evaporated films of which behave as n-type semiconductors, and can be used to fabricate thin film transistors with FET mobilities about 0.01 cm 2 /Vs.
- Novel perfluoroether acyl (oligo)thiophene compounds including ⁇ , ⁇ -bis- perfluoroether acyl oligothiophene compounds are provided. Additionally, a novel method of preparing the compounds is provided.
- the compounds are useful, for example, as n- channel semiconductor layers in electronic devices, such as thin film transistors.
- n-channel semiconductor layers in electronic devices, such as thin film transistors.
- the semiconductor devices include a semiconductor layer that contains at least one perfluoroether acyl oligothiophene compound, preferably at least one ⁇ , ⁇ -bis-perfluoroether acyl oligothiophene compound.
- novel compounds may be represented by the formula
- Y is a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a perfluoroether acyl group
- p is at least one, preferably at least two
- R f is a perfluoroether group.
- Preferred compounds are those ⁇ , ⁇ -bis-perfluoroether acyl oligothiophene compounds of Formula II:
- semiconductor devices include a semiconductor layer that contains a ⁇ , ⁇ -bis-perfluoroether acyl oligothiophene compound of Formulas I or II.
- a method of preparing a semiconductor device involves preparing a semiconductor layer that contains a compound of Formula II. The semiconductor layer is often formed using a vapor deposition technique.
- Some of the methods of preparing semiconductor devices are methods of preparing organic thin film transistors.
- One such method involves providing a gate electrode; depositing a gate dielectric layer on a surface of the gate electrode; preparing a semiconductor layer adjacent to a surface of the gate dielectric layer opposite the gate electrode; and positioning a source electrode and a drain electrode on a surface of the semiconductor layer that is opposite the gate dielectric layer.
- the source electrode and the drain electrode are separated from each other in an area on the surface of the semiconductor layer.
- the semiconductor layer contains a compound of Formulas I or II.
- An additional method of preparing an organic thin film transistor involves providing a gate electrode; depositing a gate dielectric layer on a surface of the gate electrode; positioning a source electrode and a drain electrode adjacent to the gate dielectric layer opposite the gate electrode, wherein the source electrode and the drain electrode are separated by an area over the gate dielectric layer; and preparing a semiconductor layer on the source electrode, the drain electrode, and in the area between the source electrode and the drain electrode.
- the semiconductor layer includes a compound of Formulas I or II.
- Figures Ia and b show cross-sectional representations of exemplary organic thin film transistors.
- Figure 2 is a graph of the performance of a semiconductor device of using the oligothiophene semiconductor of Example 10.
- Figure 3 is a graph of the performance of a semiconductor device using the oligothiophene semiconductor of Example 11.
- Novel perfluoroether acyl (oligo)thiophene compounds are provided.
- the novel compounds are of the general formula:
- Y is a hydrogen atom, a halogen atom, an alkyl group, and aryl group or a perfluoroether acyl group
- p is at least one, preferably at least two
- Rf is a perfluoroether group
- Preferred ⁇ , ⁇ -bis-perfluoroether acyl oligothiophene compounds are provided.
- the novel compounds are of the general formula:
- each R f is a perfluoroether group, and n is at least 2.
- the present invention provides semiconductor devices and methods of preparing semiconductor devices that include a semiconductor layer that contains a perfluoroether acyl (oligo)thiophene compound.
- Suitable thiophene groups include those having two to six successively linked thiophene rings.
- Alkyl means a saturated monovalent hydrocarbon radical having from one to about twelve carbon atoms or a branched saturated monovalent hydrocarbon radical having from three to about twelve carbon atoms, for example, methyl, ethyl, 1 -propyl, 2- propyl, pentyl, and the like.
- Alkylene means a saturated divalent hydrocarbon radical having from one to about twelve carbon atoms or a branched saturated divalent hydrocarbon radical having from three to about twelve carbon atoms, for example, methylene, ethylene, propylene, 2- methylpropylene, pentylene, hexylene, and the like.
- Alkyleneoxy has essentially the meaning given above for alkylene except the alkylene group is terminated by an oxygen atom, for example, -CH 2 CH 2 O-, - CH 2 CH 2 CH 2 O-, -CH 2 CH 2 CH 2 CH 2 O-, -CH 2 CH(CH 3 )CH 2 O-, and the like.
- aryl refers to monovalent unsaturated aromatic carbocyclic radicals having a single ring, such as phenyl, or multiple condensed rings, such as naphthyl or anthryl.
- oligothiophene refers to oligomers having at least two thiophene repeat units, linked by a covalent bond at the successive 2 positions.
- (Oligo)thiophene shall be inclusive of thiophene compounds having one thiophene ring and oligomeric thiophene compounds (oligothiophenes) having two or more thiophene rings.
- Perfluoroalkyl has essentially the meaning given above for “alkyl” except that all or essentially all of the hydrogen atoms of the alkyl radical are replaced by fluorine atoms and the number of carbon atoms is from 1 to about 12, for example, perfluoropropyl, perfluorobutyl, perfluorooctyl, and the like.
- Perfluoroalkylene has essentially the meaning given above for “alkylene” except that all or essentially all of the hydrogen atoms of the alkylene radical are replaced by fluorine atoms, for example, perfluoropropylene, perfluorobutylene, perfluorooctylene, and the like.
- Perfluoroalkyloxy has essentially the meaning given above for “alkyloxy” except that all or essentially all of the hydrogen atoms of the alkyoxy radical are replaced by fluorine atoms and the number of carbon atoms is from 3 to about 12, for example, CF 3 CF 2 O-, CF 3 CF 2 CF 2 CF 2 O-, C 3 F 7 CF(CF 3 )O-, and the like.
- Perfluoroalkyleneoxy has essentially the meaning given above for “alkyleneoxy” except that all or essentially all of the hydrogen atoms of the alkyleneoxy radical are replaced by fluorine atoms, for example, -CF 2 O-, -CF 2 CF 2 O-, -CF 2 CF(CF 3 )O-, and the like.
- Perfluoroether is a saturated, perfluoroinated monovalent alkyl radical having from 2 to about 50 carbon atoms and at least one ether oxygen atom, for example, CF 3 CF 2 OCF 2 -, CF 3 CF 2 CF 2 CF 2 OCF 2 CF 2 -, CF 3 CF(CF 3 )O CF 2 CF 2 OCF 2 CF 2 -, CF 3 CF(CF 3 )O-[CF(CF 3 )-CF 2 O] n -CF(CF 3 )-, and the like.
- Perfluoroether is inclusive of perfluoro monoethers and perfluoro poly ethers.
- Semiconductor Devices Semiconductor devices are provided that have a semiconductor layer that contains compound of the formula
- each R f is a perfluoroether group, and n is at least 2, preferably 3 to 6.
- R f may be a monoether or a polyether, that is, a monovalent perfluoroalkoxyalkylene group or a monovalent perfluoropolyether group.
- the perfluoroheteroalkyl group, R f , of the fluorinated ether of Formulas I and II preferably corresponds to the formula:
- R f 1 represents a perfluoroalkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms
- (R f 2 ) x represents a perfluoropolyalkyleneoxy group consisting of perfluoroalkyleneoxy groups
- Rf 2 having 1 to 10 perfluorinated carbon atoms, preferably 1 to 6 carbon atoms
- R f 3 represents a perfluoroalkylene group having 1 to 10 perfluorinated carbon atoms, preferably 1 to 6 carbon atoms
- x is 0 to 25, preferably at least one, more preferably 1 to 4.
- the perfluoroalkyl and perfluoroalkylene groups in formula (III) may be linear or branched.
- a typical perfluoroalkyl group is CF 3 -CF 2 -CF 2 -.
- R f 3 is -CF 2 - or -CF(CF 3 )-.
- R f 1 examples include CF 3 -CF 2 -, CF 3 -CF(CF 3 )-, CF 3 -CF 2 - CF 2 -, CF 3 -, CF 3 -CF 2 CF 2 -CF(CF 3 )-, CF 3 -CF 2 CF(C 3 F 7 )-, CF 3 -CF(C 3 F 7 )CF 2 -, and CF 3 -CF 2 - CF 2 -CF 2 -.
- perfluoroalkyleneoxy groups of perfluorinated polyalkyleneoxy group R f 2 include: -CF 2 -CF 2 -O-, -CF(CF 3 )-CF 2 -O-, -CF 2 -CF(CF 3 )-O-, -CF 2 -CF 2 -CF 2 -O-, -CF 2 -O-, -CF(CF 3 )-O-, and -CF 2 -CF 2 -CF 2 -CF 2 -O-.
- R f 3 examples include: -CF 2 -CF 2 -, -CF(CF 3 )-CF 2 -, -CF 2 -CF(CF 3 )-, -CF 2 -CF 2 -, -CF 2 -, -CF(CF 3 )-, and -CF 2 -CF 2 -CF 2 -CF 2 -.
- the perfluoroalkyleneoxy group, Rf 2 may be comprised of the same perfluoroalkyleneoxy units or of a mixture of different perfluoroalkylene oxy units.
- perfluoroalkyleneoxy group When the perfluoroalkyleneoxy group is composed of different perfluoroalkylene oxy units, they can be present in a random configuration, alternating configuration or they can be present as blocks.
- Typical examples of perfluoropolyalkyleneoxy groups include -[CF 2 -CF 2 -O] n -; -[CF(CF 3 KF 2 -O] n -; -[CF 2 CF 2 -O]i-[CF 2 O] r and -[CF 2 -CF 2 -O],-[CF(CF 3 )-CF 2 -O] m -; wherein n is an integer of 1 to 25, and i, 1, m and j each are integers of 1 to 25.
- the fluorinated polyether, R f corresponds to the following formula (IV):
- a preferred perfluorinated polyether group that corresponds to formula (IV) is CF 3 -CF(CF 3 )-O-[CF(CF 3 )-CF 2 O] X -CF(CF 3 )- wherein x is an integer of 1 to 4.
- This perfluoropolyether can be derived from an oligomerization of hexafluoropropylene oxide.
- Preferred perfluoroether groups, R f are dimers, trimers and tetramers derived from the hexafluoropropylene oxide (HFPO) and correspond to the structures: F(CFCF 2 O) 1-4 CF- CF 3 CF 3
- the corresponding acids, acid halides and esters may be prepared from the oligomerization of hexafluoropropylene oxide, or the oxidative oligomerization of hexafluoropropylene, such as is known in the art. Many of these compounds are commercially available from Matrix Scientific, Columbia, SC. Compounds according to formula (IV) can for example be obtained by oligomerization of hexafluoropropylene oxide, which results in a perfluoropolyether carbonyl fluoride. This carbonyl fluoride may be converted into an acid, or ester by reactions well known to those skilled in the art.
- the carbonyl fluoride or acyl fluoride, acid, or ester derived therefrom may then be reacted further to introduce the desired perfluoroether groups into the oligothiophene compounds according to known acylation procedures.
- U.S. 6,127,498 or U.S. 3,536,710 describe suitable methods to produce compounds according to formula (IV) having desired acyl moieties.
- Perfluoroether acyl (oligo)thiophene compounds of Formula I, where Y is not a perfluoroether acyl group may be prepared as follows.
- the corresponding 2- bromo-5-perfluoroether acyl compound may be prepared by monoacylation of 2,5- dibromothiophene to directly produce the 2-bromo-5-perfluoroether acyl compound.
- thiophene compounds where Y is H, halogen, alkyl or aryl may be prepared by Stille coupling of a thienyl stannane with an ⁇ -bromo- ⁇ -perfluoroether acyl thiophene according to the following general scheme:
- Preferred ⁇ , ⁇ -bis-perfmoroether acyl oligothiophene compounds of Formula II may be prepared according to Reaction Scheme A by a Stille coupling reaction.
- the oligothiophenes may be prepared by reacting a bis(trialkylstannyl)thiophene (such as a 2,5-bis(trialkylstannyl)thiophene or a 5,5'- bis(trialkylstannyl)bithiophene) with a 2-perfluoroether acyl 5-halothiophene (or a 5- perfluoroether acyl 5'-halobithiophene) in the presence of a palladium catalyst.
- a bis(trialkylstannyl)thiophene such as a 2,5-bis(trialkylstannyl)thiophene or a 5,5'- bis(trialkylstannyl)bithiophene
- a 2-halo-5-perfluoroetheracyl thiophene (such compounds of formulas VI) or a 5- halo-5'-perfluoroetheracylbithiophene (such compounds of formulas X) can be reacted with a bis(trialkylstannyl) compound (that is, Formula V or VIII, where R is an alkyl group) to form a ⁇ , ⁇ -bis(2-perfluoroetheracyl oligothiophene (that is, Formula VII, IX, XI or XII).
- the Stille coupling reaction may be performed as outlined in Farina V. and Krishnamurthy, V. in Organic Reactions; L.A. Paquette, Ed., John Wiley and Sons., 1997; vol. 50, pp. 1-652.
- the reaction products may be purified to a semiconductor grade material by any known process such as by vacuum sublimation.
- the bis-trialkylstannyl thiophene compounds of formulas V and VIII are known. Reference may be made to Y. Wei et al. Chem. Mater. Vol. 8, 1996, pp.2659-2666.
- the monoacyl compound of formula VI may be made by treatment of 2,5- dihalothiophene with an alkyl lithium compound, to produce the 2-bromo-5-lithio thiophene, followed by reaction with a perfluorinated ether ester (or equivalent) in the presence of boron trifluoride etherate.
- This method yields the desired product V in high yields, and has proven superior to other known methods, such as formation of the cuprate, followed by reaction with a perfluorinated acyl compound.
- the monoacyl bithiophene compound X may be prepared by a two-step synthesis comprising first reacting 5-lithio-2,2'-bithiophene (generated in situ) with a perfluorinated ether ester (or equivalent) in the presence of boron trifluoride etherate), followed by bromination, such as by N-bromosuccinimide.
- 5-halo-5'-perfluoroether acyl thiophene compounds are useful in the preparation of the bis-perfluoroether thiophene compounds of the present invention.
- Such novel compounds are of the general formula:
- Y is H, a halogen, an aryl or an alkyl group
- Rf is a perfluoroether group
- p is 1 to 6
- Compounds where p is 2 or greater may be prepared by a Stille coupling reaction of a compound of formula VI or X with a mono-trialkylstannyl thiophene or a mono- trialkylstannyl bithiophene, followed by halogenation of the ⁇ -5 position of the terminal thiophene ring.
- the bithiophene compound of formula XIII may be prepared by coupling of the 5- bromo-2-thienyl magnesium bromide and a perfluoroether acid halide according to the procedure described in Portnoy, J. Org. Chem, vol. 32, 1967, pp 233-4. The Ullman coupling reactions may also prove useful.
- Asymmetric ⁇ , ⁇ -bis-perfluoroether acyl oligothiophenes that is, a oligothiophenes with different perfluoroether acyl groups can be prepared, for example, through using a mixture of compounds of Formulas VI or X having different R f groups, although a mixture of products will result.
- the preferred bromo-substituted thiophenes are illustrated, but other halides may also be used.
- the compounds of the invention may be used as a n-channel semiconductor.
- the semiconductor layer that contains a ⁇ , ⁇ -bis-perfluoroether acyl oligothiophene compound can be included in any type of semiconductor device.
- Semiconductor devices have been described, for example, by S. M. Sze in Physics of Semiconductor Devices. 2 nd edition, John Wiley and Sons, New York (1981). Such devices may include rectifiers, transistors (of which there are many types, including p-n-p, n-p-n, and thin-film transistors), photoconductors, current limiters, thermistors, p-n junctions, field-effect diodes, Schottky diodes, and the like.
- Semiconductor devices can include components such as transistors, arrays of transistors, diodes, capacitors, embedded capacitors, and resistors that are used to form circuits. Semiconductor devices also can include arrays of circuits that perform an electronic function. Examples of these arrays, or integrated circuits, are inverters, oscillators, shift registers, and logic. Applications of these semiconductor devices and arrays include radio frequency identification devices (RPIDs), smart cards, displays backplanes, sensors, memory devices, and the like.
- RIDs radio frequency identification devices
- Each semiconductor device contains a semiconductor layer with a compound according to Formulas I or II.
- the semiconductor layer can be combined with a conductive layer, a dielectric layer, or a combination thereof to form the semiconductor device.
- Semiconductor devices can be prepared or manufactured by known methods such as, for example, those described by Peter Van Zant in Microchip Fabrication, Fourth Edition, McGraw-Hill, New York (2000).
- the organic thin-film transistor (OTFT) 10 includes an optional substrate 12, a gate electrode 14 disposed on the optional substrate 12, a gate dielectric material 16 disposed on the gate electrode 14, an optional surface treatment layer 18 disposed on the gate dielectric layer 16, a source electrode 22, a drain electrode 24, and a semiconductor layer 20 that is in contact with both the source electrode 22 and the drain electrode 24.
- the source electrode 22 and the drain electrode 24 are separated from each other in an area on the surface of the semiconductor layer 20 (that is, the source electrode 22 does not contact the drain electrode 24).
- the portion of the semiconductor layer that is positioned between the source electrode and the drain electrode is referred to as the channel 21.
- the channel is positioned over the gate electrode 14, the gate dielectric layer 16, and the optional surface treatment layer 18.
- the semiconductor layer 20 contacts the gate dielectric layer 16 or the surface treatment layer 18.
- FIG. Ib A second embodiment of an organic thin-film transistor is shown in Figure Ib.
- This OTFT 100 includes a gate electrode 14 disposed on an optional substrate 12, a gate dielectric layer 16 disposed on the gate electrode 14, an optional surface treatment layer 18 disposed on the gate dielectric layer 16, a semiconductor layer 20, and a source electrode 22 and a drain electrode 24 disposed on the semiconductor layer 20.
- the semiconductor layer 20 is between the gate dielectric layer 16 and both the source electrode 22 and the drain electrode 24.
- the semiconductor layer 20 can contact the gate dielectric layer 16 or the optional surface treatment layer 18.
- the source electrode 22 and the drain electrode 24 are separated from each other (that is, the source electrode 22 does not contact the drain electrode 24) in an area on the surface of the semiconductor layer 20.
- the channel 21 is the portion of the semiconductor layer that is positioned between the source electrode 22 and the drain electrode 24.
- the channel 21 is positioned over the gate electrode 14, the gate dielectric layer 16, and the optional surface treatment layer 18.
- a substrate 12 often supports the OTFT during manufacturing, testing, and/or use.
- the substrate can provide an electrical function for the OTFT.
- the backside of the substrate can provide electrical contact.
- Useful substrate materials include, but are not limited to, inorganic glasses, ceramic materials, polymeric materials, filled polymeric materials (for example, fiber-reinforced polymeric materials), metals, paper, woven or non-woven cloth, coated or uncoated metallic foils, or a combination thereof.
- Suitable polymeric substrates include acrylics, epoxies, polyamides, polycarbonates, polyimides, polyketones, polynorbornenes, polyphenyleneoxides, poly(ethylene naphthalate), poly(ethylene terephthalate), poly(phenylene sulfide), poly(ether ether ketones) such as poly(oxy-l,4-phenyleneoxy-l,4-phenylenecarbonyl-l,4- phenylene), and the like.
- the gate electrode 14 can include one or more layers of a conductive material.
- the gate electrode can include a doped silicon material, a metal, an alloy, a conductive polymer, or a combination thereof.
- Suitable metals and alloys include, but are not limited to, aluminum, chromium, gold, silver, nickel, palladium, platinum, tantalum, titanium, indium tin oxide (ITO) or a combination thereof.
- Exemplary conductive polymers include, but are not limited to, polyaniline or poly(3,4- ethylenedioxythiophene)/poly(styrene sulfonate).
- the same material can provide both the gate electrode function and the support function of the substrate.
- doped silicon can function as both the gate electrode and as a substrate.
- the gate dielectric layer 16 is disposed on the gate electrode 14. This gate dielectric layer 16 electrically insulates the gate electrode 14 from the balance of the OTFT device.
- Useful materials for the gate dielectric include, for example, an inorganic dielectric material, a polymeric dielectric material, or a combination thereof.
- the gate dielectric can be a single layer or multiple layers of suitable materials. Each layer in a single or multilayer dielectric can include one or more dielectric materials.
- Exemplary inorganic dielectric materials include strontiates, tantalates, titanates, zirconates, aluminum oxides, silicon oxides, tantalum oxides, titanium oxides, silicon nitrides, barium titanate, barium strontium titanate, barium zirconate titanate, zinc selenide, zinc sulfide, hafnium oxides, and the like.
- alloys, combinations, and multiple layers of these materials can be used for the gate dielectric layer 16.
- Exemplary polymeric dielectric materials include polyimides, parylene C, crosslinked benzocyclobutene, cyanoethylpullulan, polyvinyl alcohol, and the like. See, for example, CD. Sheraw et al., "Spin-on polymer gate dielectric for high performance organic thin film transistors", Materials Research Society Symposium Proceedings, vol. 558, pages 403-408 (2000), Materials Research Society, Warrendale, PA, USA; and U.S. Patent No. 5,347,144 (Gamier).
- organic polymeric dielectrics include cyano-functional polymers such as cyano-functional styrenic copolymers as disclosed in U.S. Patent Application Serial No. 10/434,377, filed May 8, 2003. Some of these polymeric materials can be coated from solution, can be crosslinked, can be photo-patterned, can have high thermal stability (for example, stable up to a temperature of about 250 0 C), can have a low processing temperature (for example, less than about 150 0 C or less than about 100 0 C), can be compatible with flexible substrates, or combinations thereof.
- cyano-functional polymers such as cyano-functional styrenic copolymers as disclosed in U.S. Patent Application Serial No. 10/434,377, filed May 8, 2003.
- Exemplary cyano-functional polymers that can be used as organic dielectric materials include, but are not limited to, styrene maleic anhydride copolymers modified by adding a methacrylate functional group for crosslinking purposes and by attaching cyano- functional groups; the reaction product of bis(2-cyanoethyl)acrylamide with an acrylated polystyrene macromer; polymers formed from 4-vinylbenzylcyanide; polymers formed from 4-(2,2'-dicyanopropyl)styrene; polymers formed from 4-(l,l ',2- tricyanoethyl)styrene; and polymers formed from 4-(bis-(cyanoethyl)aminoethyl)styrene; and a copolymer formed from 4-vinylbenzylcyanide and 4-vinylbenzylacrylate.
- the organic thin film transistors can include an optional surface treatment layer 18 disposed between the gate dielectric layer 16 and at least a portion of the organic semiconductor layer 20.
- the optional surface treatment layer 18 serves as an interface between the gate dielectric layer and the semiconductor layer.
- the surface treatment layer can be a self-assembled monolayer or a polymeric material.
- Suitable self-assembled monolayer surface treatment layers are disclosed, for example, in U.S. Patent No. 6,433,359 Bl (Kelley et al.).
- Exemplary self-assembled monolayers can be formed from l-phosphono-2-ethylhexane, l-phosphono-2,4,4- trimethylpentane, l-phosphono-3,5,5-trimethylhexane, 1 -phosphonoctane, 1- phosphonohexane, 1-phosphonohexadecane, l-phosphono-3,7,11,5- tetramethylhexadecane, and the like.
- Useful polymers and copolymers for a surface treatment layer are usually non- polar, glassy solids at room temperature.
- the polymeric materials in this layer typically have glass transition temperature (T g ) measured in the bulk of at least 25 °C, of at least 50 °C, or of at least 100 0 C.
- T g glass transition temperature
- Suitable polymeric surface treatment layers are described, for example, in U.S. Patent Application Publication 2003/0102471 Al (Kelley et al.) and U.S. Patent No. 6,617,609 (Kelley et al.)
- Exemplary polymeric surface treatment layers can contain polystyrene, polyfluorene, polynorbornene, poly(l-hexene), poly(methyl methacrylate), poly(acenaphthylene), poly(vinylnaphthalene), poly(butadiene), and polyvinyl acetate).
- Other exemplary polymeric surface treatment layers can contain polymers or copolymers derived from ⁇ -methylstyrene, 4-tert-butylstyrene, 2-methylstyrene, 3-methylstyrene, 4- methylstyrene, 4-(phosphonomethyl)styrene, divinyl benzene, and combinations thereof.
- Examples of still other useful polymeric materials for the surface treatment layer include poly(dimethylsiloxane), poly(dimethylsiloxane-co-diphenylsiloxane), poly(methylphenylsiloxane-co-diphenylsiloxane), poly(dimethylsiloxane-co- methylphenylsiloxane), and the like.
- the surface treatment layer often has a maximum thickness less than 400 Angstroms (A).
- the surface treatment layer can be less than 200 A, less than 100 A, or less than 50 A.
- the surface treatment layer generally has a thickness of at least about 5 A, at least about 10 A, or at least 20 A. The thickness can be determined through known methods such as ellipsometry.
- the source electrode 22 and drain electrode 24 can be metals, alloys, metallic compounds, conductive metal oxides, conductive ceramics, conductive dispersions, and conductive polymers, including, for example, gold, silver, nickel, chromium, barium, platinum, palladium, aluminum, calcium, titanium, indium tin oxide (ITO), fluorine tin oxide (FTO), antimony tin oxide (ATO), indium zinc oxide (IZO), poly(3,4- ethylenedioxythiophene)/poly(styrene sulfonate), polyaniline, other conducting polymers, alloys thereof, combinations thereof, and multiple layers thereof.
- ITO indium tin oxide
- FTO fluorine tin oxide
- ATO antimony tin oxide
- IZO indium zinc oxide
- IZO indium zinc oxide
- polyaniline other conducting polymers, alloys thereof, combinations thereof, and multiple layers thereof.
- the thin film electrodes (for example, the gate electrode, the source electrode, and the drain electrode) can be provided by any means known in the art such as physical vapor deposition (for example, thermal evaporation or sputtering), ink jet printing, or the like.
- the patterning of these electrodes can be accomplished by known methods such as shadow masking, additive photolithography, subtractive photolithography, printing, microcontact printing, and pattern coating.
- the semiconductor devices that contain the perfluoroether acyl oligothiophene compounds tend to have performance characteristics such as charge-carrier mobility and current on/of ratio that are comparable to known organic semiconductor devices such as those that contain pentacene.
- semiconductor devices can be prepared that have an n-channel mobility of about 1 cm /volt-sec and on-off ratio greater than about 10 .
- a method of preparing a semiconductor device involves preparing a semiconductor layer that contains a perfluoroether acyl oligothiophene compound of Formulas I or II, where n is preferably 3 to 6.
- the semiconductor layer is usually formed using a vapor deposition process.
- the method involves preparing a semiconductor layer that contains a perfluoroether acyl oligothiophene compound of Formulas I or II; and depositing a dielectric layer, a conductive layer, or a combination thereof adjacent to the semiconductor layer.
- adjacent refers to a first layer that is positioned near a second layer. The first layer often contacts the second layer but another layer could be positioned between the first and second layer. No specific order of preparing or depositing is necessary; however, the semiconductor layer is often prepared on the surface of another layer such as the dielectric layer, conductive layer, or a combination thereof.
- One exemplary method of preparing a semiconductor device provides an organic thin film transistor.
- the method includes preparing a semiconductor layer that contains a perfluoroether acyl oligothiophene compound of Formulas I or II; positioning a source electrode and a drain electrode on a surface of the semiconductor layer such that the source electrode and the drain electrode are separated in an area on the surface of the semiconductor layer (that is, the source electrode does not contact the drain electrode).
- the method can further include providing a gate dielectric layer, a gate electrode, and an optional surface treatment layer.
- an organic thin film transistor can be prepared by providing a gate electrode; depositing a gate dielectric layer on a surface of the gate electrode; preparing a semiconductor layer adjacent to the gate dielectric layer (that is, the gate dielectric is positioned between the gate electrode and the semiconducting layer); and positioning a source electrode and a drain electrode on a surface of the semiconductor layer that is opposite the gate dielectric layer.
- the source electrode and the drain electrode are separated from each other in an area on the surface of the semiconductor layer.
- the various layers of the semiconductor device are arranged in the following order: gate electrode; gate dielectric layer; semiconductor layer; and a layer containing a source electrode and a drain electrode.
- the various layers of the semiconductor device are arranged in the following order: gate electrode, gate dielectric layer, surface treatment layer, semiconductor layer, and a layer containing a source electrode and a drain electrode.
- the source electrode does not contact the drain electrode in these embodiments. That is, the source electrode and the drain electrode are separated from each other in an area on the surface of the semiconductor device.
- One surface of the semiconductor layer contacts both the source electrode and the drain electrode while the opposite surface of the semiconductor layer contacts the gate dielectric layer or the surface treatment layer.
- the organic thin film transistor exemplified in Figure Ib can be prepared by providing a substrate, depositing a gate electrode on the substrate, depositing a gate dielectric layer on a surface of the gate electrode such that the gate electrode is positioned between the substrate and the gate dielectric layer; applying a surface treatment layer to a surface of the gate dielectric layer opposite the gate electrode; preparing a semiconductor layer on a surface of the surface treatment layer opposite the gate dielectric layer; and positioning a source electrode and a drain electrode on a surface of the semiconductor layer that is opposite the polymeric treatment layer.
- the source electrode and the drain electrode are separated from each other in an area on the surface of the semiconductor layer. The area of separation between the source electrode and the drain electrode can define a channel in the semiconductor layer.
- Another organic thin film transistor can be prepared by providing a gate electrode; depositing a gate dielectric layer on a surface of the gate electrode; positioning a source electrode and a drain electrode adjacent to the gate dielectric material such that the source electrode and the drain electrode are separated from each other in an area over the gate dielectric layer; preparing a semiconductor layer that is deposited on the source electrode, drain electrode, and in the area between the source electrode and the drain electrode. The semiconductor layer contacts both the source electrode and the drain electrode. The portion of the semiconductor layer that is positioned in the area between the source electrode and the drain electrode defines the channel.
- the various layers of the semiconductor device are arranged in the following order: gate electrode; gate dielectric layer; a layer containing a source electrode and a drain electrode; and a semiconductor layer.
- the various layers of the semiconductor device are arranged in the following order: gate electrode; gate dielectric layer; surface treatment layer; a layer containing a source electrode and a drain electrode; and semiconductor layer.
- the source electrode does not contact the drain electrode in these embodiments.
- a portion of the semiconductor layer can extend between the source electrode and the drain electrode.
- the organic thin film transistor exemplified in Figure Ia can be prepared by providing a substrate, depositing a gate electrode on the substrate, depositing a gate dielectric layer on a surface of the gate electrode such that the gate electrode is positioned between the substrate and the gate dielectric layer; applying a surface treatment layer to a surface of the gate dielectric layer opposite the gate electrode; positioning a source electrode and a drain electrode on a surface of the polymeric treatment layer such that the two electrodes are separated from each other in an area; preparing a semiconductor layer on the source electrode, drain electrode, and in the area between the source electrode and the drain electrode.
- the semiconductor layer contacts both the source electrode and the drain electrode.
- the portion of the semiconductor layer that is positioned in the area between the source electrode and the drain electrode defines a channel in the semiconductor layer.
- the organic thin film transistors or other semiconductor devices such as integrated circuits can be prepared using flexible, repositionable polymeric aperture masks.
- the technique involve sequentially depositing material through a number of polymeric aperture masks formed with patterns that define layers, or portions of layers, of the semiconductor device.
- the use of such polymeric aperture masks are further described in U.S. Patent Publication Nos. 2003/0094959-A1, 2003/0150384-A1, 2003/0152691-A1, and 2003/0151118-Al.
- Repositionable polymeric aperture masks often have a thickness of 5 to 50 micrometers or 15 to 35 micrometers.
- the various deposition apertures in the aperture masks usually have widths less than 1000 micrometers, less than 50 micrometers, less than 20 micrometers, less than 10 micrometers, or even less than 5 micrometers. Apertures of these sizes are particularly useful in creating small circuit elements for integrated circuits. Moreover, one or more gaps between deposition apertures are typically less than 1000 micrometers, less than 50 micrometers, less than 20 micrometers, or less than 10 micrometers, which is also useful in creating small circuit elements.
- the aperture masks can have a pattern with a width greater than 1 centimeter, 25 centimeters, 100 centimeters, or even 500 centimeters. Patterns having these widths can be useful in creating various circuits over a larger surface area.
- Various laser ablation techniques may be used to facilitate the creation of polymeric aperture masks having patterns of deposition apertures.
- stretching techniques and other techniques may be used to facilitate alignment of flexible polymeric aperture masks.
- methods of controlling sag in aperture masks may be used which can be particularly useful in using masks that include a pattern that extends over a large width.
- Other methods known in the art can be used to prepare the semiconductor devices. These methods include, for example, metal shadow masks; photolithography and/or etching; and printing methods such as inkjet, screen-printing, gravure printing, and the like. In some methods that involve the use of aperture masks, semiconductor devices
- circuits for example, integrated circuits
- the techniques can be particularly useful in creating circuit elements for electronic displays such as liquid crystal displays and low-cost integrated circuits such as radio frequency identification (RPID) circuits.
- RPID radio frequency identification
- such techniques can be advantageous in the fabrication of integrated circuits incorporating organic semiconductors, which typically are not compatible with photolithography or other wet chemical processes.
- Tetrahydrofuran (THF) and diethyl ether (Et 2 O) were distilled from sodium/benzophenone ketyl.
- N,N-dimethylformamide (DMF) was vacuum distilled under nitrogen from MgSO 4 or purchases as anhydrous grade from Aldrich. All other solvents were used as obtained.
- Bithiophene, 2,5-dibromothiophene, 3- bromothiophene, boron trifluoride diethyl etherate, aluminum trichloride, /-z-butyl lithium (1.6 M or 2.5 M in hexanes), iV-bromosuccimide (NBS), and dimethylamine borane were purchased from Aldrich.
- NBS was recrystallized from hot water and dried under vacuum prior to use.
- Perfluoro(2,5-dimethyl-3,6-dioxanonanoic) acid methyl ester (HFPO trimer carbomethoxylate), methyl 3,6-dioxadecanoate, and methyl 3,6,9-trioxadecanoate were purchased from Matrix Scientific (Columbia, SC) and used as received.
- Tetrakis(triphenylphosphine)palladium (0) was purchased from Strem Chemicals, Newburyport, MA.
- IR 1684 (v co ), 1505 w, 1450 m, 1423w, 1229 s, 1193 s, 1139 s, 1103 s, 1077 s, 906 m, 869 m, 842 m, 803 m, 741 m, 706 s, 682 m, 619 w, 546 w, 522 w, 508 w, 453 w cm "1 .
- This compound was prepared analogously to Example 1.
- a reaction between BuLi (36.75 rnL, 58.8 mmol) and bithiophene (9.75 g, 58.6 mmol) in cold THF (250 mL, -70 °C) was stirred for 30 min, followed by a sequential addition of C 4 F 9 OC 2 F 4 OCF 2 CO 2 Me (30.2 g , 65.7 mmol) and BF 3 OEt 2 (9.0 mL, 71 mmol).
- IR 1666 s (v ⁇ ), 1504 w, 1449 S 5 1310 s, 1233 s, 1202 vs, 1153 s, 1081 m,1027 m, 993 s, 897 w, 850 m, 837 m, 802 s, 763 m. 752 m, 721 m, 710 S 5 654 m, 616 m,532 m, 456 w cm "1 .
- NBS (2.50 g, 13.32 mmol) was added to a stirred mixture of DMF (250 mL) and 5-perfluoro(3,6 5 9-trioxadecanoyl)-2 5 2 '-bithiophene (6.22 g 5 11.1 mmol) that was covered with aluminum foil.
- the solution was stirred overnight, poured into 500 mL of brine, and extracted with Et 2 O (500 mL) and hexanes (250 mL). The yellow extract was separated, washed with 100 mL brine, 100 mL water, dried with MgSO 4 , and filtered.
- a DMF solution (200 niL) of 5-perfiuoro(3,6-dioxadecanoyl)-2,2'-bithiophene (17.20 g, 28.94 mmol) was charged with NBS (6.70 g, 37.6 mrnol) and stirred overnight covered with foil. Orange crystals of the product precipitated from the solution.
- Et 2 O (200 mL) and brine (200 niL) were added to the reaction and the solution washed in a separatory funnel. The organic layer was separated and washed with 3 x 200 mL of brine.
- IR 1671 s, 1508 w, 1446 s, 1420 w, 1337 w, 1312 m, 1290 w, 1219 s, 1192 s, 1144 s, 1114 m, 1082 m, 975 w, 954 w, 901 w, 891 w, 860 w, 821 w, 788 m, 736 w, 714 w, 693 w, 684 w, 649 w, 597 w, 543 w, 509 w, 457 w, 409 w cm "1 .
- BuLi (7.8 niL, 12.5 mmol) was added to a cold (-65 0 C) mixture of THF (50 niL) and thiophene (1.0 mL, 12.5 mmol.
- the clear, colorless solution was warmed to room temperature, cooled to -65 0 C, and C 4 F 9 OC 2 F 4 OCF 2 CO 2 Me (5.84 g, 12.7 mmol) and BF 3 (OEt 2 ) (1.9 mL, 15 mmol) added successively.
- the yellow solution was stirred cold for 2 hr and then mixed with 2 mL of saturated NH 4 Cl (aq). The volatile material was removed under reduced pressure, and the residue extracted with 50 mL hexanes.
- reaction mixture was transferred into a mixture of EtOAc (100 mL) and CH 2 Cl 2 (100 mL), stirred, and then poured through a 10- 20 ⁇ m glass filter frit to isolate the product. The red solid was washed on the frit with methanol (100 mL) and air-dried overnight to afford 2.28 g (70%).
- High performance liquid chromatography with a THF solution of the product was carried out using an Agilent Model LC/MSD quadrupole mass spectrometer equipped with an atmospheric pressure chemical ionization (APCI) source.
- the sample solution was injected into a mobile phase of THF/water (1:1) and data were collected over the mass range of 1,000-2,000 Daltons at a scan rate of approximately 2 scans/second.
- the only significant ions in the spectrum were seen a m/z 1451, m/z 1452, and m/z 1453, corresponding to a compound having a molecular eight of 1,450, consistent with the proposed product.
- OTFTs were fabricated on doped silicon ⁇ 100> wafers obtained from Silicon Valley Microelectronics (San Jose, CA) with 5 kA aluminum on the backside and 1.5 kA of sputtered AI2O3 on the front.
- a 0.1 wt % solution of poly( ⁇ -methylstyrene) (average Mw ca 100,300 by GPC) was applied to the surface from toluene by spin coating (500 rpm for 20 s, followed by 2000 rpm for 40 s). Samples were placed in a 110 °C oven and baked for 30 min after spin coating. The resultant polymer layer was about 100 A, as measured by single beam ellipsometry.
- Thin films ( ⁇ 600 A) of the perfluoroacyl thiophenes described above were deposited by physical vapor deposition at a pressure ⁇ 5 x 10 "" Torr. Samples were then moved to another vacuum chamber where gold source-drain contacts (600 A) were evaporated on to the organic film through a polymeric shadow mask.
- Figure 2 shows characterization data (/ D 1/2 VS VQ curves calculated from I D -V G transfer curves) for thin film transistors made using 5,5'"-bis[perfluoro(3,6- dioxadecanoyl)]-2,2':5',2":5",2'"-quaterthiophene (Example 10) in the semiconductor layer.
- the data is in the saturated regime, with drain voltages (F D ) equal to the maximum gate voltage (V G ) in each case.
- the devices were measured under 10 "6 torr vacuum. Data is plotted for both negative-to-positive (-/+) and positive-to-negative (+/-) scans of the gate voltage.
- the saturation electron mobility (/Ve) was calculated from the slope of the / D 1/2 VS VQ trace at the points indicated using standard metal-oxide-semiconductor field- effect transistor (MOSFET) equations (See Sze, S. M. Physics of Semiconductor Devices; 2nd ed.; John Wiley & Sons: New York, 1981).
- MOSFET metal-oxide-semiconductor field- effect transistor
- the mobility was 1.8 cm 2 /Vs for a negative-to-positive V G scan, and 2.6 cm 2 /Vs for a positive- to-negative scan. Additional data for other devices on the same wafer are tabulated in Table 1.
- Figure 3 shows / D 1/2 VS VQ curves for a thin film transistor made using 5,5""- bis[perfluoro(3,6,9-trioxadecanoyl)]- 2,2':5',2":5",2'":5'",2""-quinquethiophene (Example 11) in the semiconductor layer.
- Devices were fabricated and tested as described above. Table 2 lists additional data for other devices on the same wafer.
- the resulting mobility values are the highest values reported to date for n-channel organic semiconductor materials, and are comparable in performance to p-channel semiconductors such as pentacene.
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Abstract
Semiconductor devices are described that include a semiconductor layer that comprises a perfluoroether acyl oligothiophene compound, preferably an α,ω-bis-perfluoroether acyl oligothiophene compound. Additionally, methods of making semiconductor devices are described that include depositing a semiconductor layer that contains a perfluoroether acyl oligothiophene compound, preferably an α,ω-bis(2- perfluoroether acyl oligothiophene compound.
Description
Semiconductors Containing Perfluoroether Acyl Oligothiophene Compounds
Technical Field The present invention provides semiconductor devices and methods of making semiconductor devices that include a semiconductor layer that contains a perfluoroether acyl oligothiophene compound.
Background Traditionally, inorganic materials have dominated the semiconductor industry. For example, silicon arsenide and gallium arsenide have been used as semiconductor materials, silicon dioxide has been used as an insulator material, and metals such as aluminum and copper have been used as electrode materials. In recent years, however, there has been an increasing research effort aimed at using organic materials rather than the traditional inorganic materials in semiconductor devices. Among other benefits, the use of organic materials may enable lower cost manufacturing of electronic devices, may enable large area applications, and may enable the use of flexible circuit supports for display backplanes or integrated circuits.
A variety of organic semiconductor materials have been considered, the most common being fused aromatic ring compounds as exemplified by tetracene and pentacene, bis(acenyl)acetylene, and acene-thiophenes; oligomeric materials containing thiophene or fluorene units; and polymeric materials such as regioregular poly(3-alkylthiophene). At least some of these organic semiconductor materials have performance characteristics such as charge-carrier mobility, on/off current ratios, and sub-threshold voltages that are comparable or superior to those of amorphous silicon-based devices.
Thiophene chemistry and the chemical stability of the thiophene ring hold potential for use of thiophene materials in molecular-based electronics and photonics. In particular, α,α'-conjugated thiophene oligomers (nTs) and polymers (polythiophenes-PTs) have attracted great interest as semiconducting elements in organic thin-film transistors (TFTs). To be useful in such devices and related structures, the organic material must support a channel of holes or electrons (p- or n-type semiconductor, respectively) created by the gate electrode bias, which switches the device "on". Furthermore, the charge mobility of the
material must be sufficiently large to increase the source-drain on-conduction by many orders of magnitude over the "off state. The density of the charge carrier in the channel is modulated by voltage applied at the gate electrode
U.S. 6,585,914 (Marks et al.) describe α,ω-diperfluoroalkylsexithiophene- evaporated films of which behave as n-type semiconductors, and can be used to fabricate thin film transistors with FET mobilities about 0.01 cm2 /Vs.
Summary
Novel perfluoroether acyl (oligo)thiophene compounds, including α,ω-bis- perfluoroether acyl oligothiophene compounds are provided. Additionally, a novel method of preparing the compounds is provided. The compounds are useful, for example, as n- channel semiconductor layers in electronic devices, such as thin film transistors. There are a considerable number of problems and deficiencies associated with the prior art relating to useful organic n-type semiconductor compounds, compositions and/or materials. There is a demonstrated need for such materials, compositions, layers and/or composites for thin film deposition and related applications useful in conjunction with the fabrication of thin film transistors and related devices as can be incorporated into an integrated circuit. Accordingly, it is an object of the present invention to provide new and useful n-type organic materials, together with one or more methods of preparation. Semiconductor devices and methods of making the semiconductor devices are provided. More specifically, the semiconductor devices include a semiconductor layer that contains at least one perfluoroether acyl oligothiophene compound, preferably at least one α,ω-bis-perfluoroether acyl oligothiophene compound.
The novel compounds may be represented by the formula
wherein Y is a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a perfluoroether acyl group, p is at least one, preferably at least two, and Rf is a perfluoroether group.
Preferred compounds are those α,ω-bis-perfluoroether acyl oligothiophene compounds of Formula II:
wherein each Rf is a perfluoroether group, and n is at least 1, preferably at least 2, more preferably 3 to 6. Using the conventional nomenclature, the successive thiophene rings are connected by a covalent bond, as indicated in Formulas I and II. In one aspect, semiconductor devices are provided that include a semiconductor layer that contains a α,ω-bis-perfluoroether acyl oligothiophene compound of Formulas I or II. In another aspect, a method of preparing a semiconductor device is provided. The method involves preparing a semiconductor layer that contains a compound of Formula II. The semiconductor layer is often formed using a vapor deposition technique.
Some of the methods of preparing semiconductor devices are methods of preparing organic thin film transistors. One such method involves providing a gate electrode; depositing a gate dielectric layer on a surface of the gate electrode; preparing a semiconductor layer adjacent to a surface of the gate dielectric layer opposite the gate electrode; and positioning a source electrode and a drain electrode on a surface of the semiconductor layer that is opposite the gate dielectric layer. The source electrode and the drain electrode are separated from each other in an area on the surface of the semiconductor layer. The semiconductor layer contains a compound of Formulas I or II.
An additional method of preparing an organic thin film transistor involves providing a gate electrode; depositing a gate dielectric layer on a surface of the gate electrode; positioning a source electrode and a drain electrode adjacent to the gate dielectric layer opposite the gate electrode, wherein the source electrode and the drain electrode are separated by an area over the gate dielectric layer; and preparing a semiconductor layer on the source electrode, the drain electrode, and in the area between the source electrode and the drain electrode. The semiconductor layer includes a compound of Formulas I or II.
The above summary of the present invention is not intended to describe each disclosed embodiment or every implementation of the present invention. The Figures, Detailed Description, and Examples that follow more particularly exemplify these embodiments. While the invention is amenable to various modifications and alternative forms, specifics thereof have been shown by way of example in the drawings and will be described in detail. It should be understood, however, that the intention is not to limit the invention to the particular embodiments described. On the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Brief Description of the Drawings
The invention may be more completely understood in consideration of the following detailed description of various embodiments of the invention in connection with the accompanying drawings, in which:
Figures Ia and b show cross-sectional representations of exemplary organic thin film transistors.
Figure 2 is a graph of the performance of a semiconductor device of using the oligothiophene semiconductor of Example 10.
Figure 3 is a graph of the performance of a semiconductor device using the oligothiophene semiconductor of Example 11.
Detailed Description
Novel perfluoroether acyl (oligo)thiophene compounds are provided. The novel compounds are of the general formula:
wherein Y is a hydrogen atom, a halogen atom, an alkyl group, and aryl group or a perfluoroether acyl group, p is at least one, preferably at least two, and Rf is a perfluoroether group.
Preferred α,ω-bis-perfluoroether acyl oligothiophene compounds are provided. The novel compounds are of the general formula:
wherein each Rf is a perfluoroether group, and n is at least 2.
The present invention provides semiconductor devices and methods of preparing semiconductor devices that include a semiconductor layer that contains a perfluoroether acyl (oligo)thiophene compound. Suitable thiophene groups include those having two to six successively linked thiophene rings.
Definition
As used herein, the terms "a", "an", and "the" are used interchangeably with "at least one" to mean one or more of the elements being described.
"Alkyl" means a saturated monovalent hydrocarbon radical having from one to about twelve carbon atoms or a branched saturated monovalent hydrocarbon radical having from three to about twelve carbon atoms, for example, methyl, ethyl, 1 -propyl, 2- propyl, pentyl, and the like. "Alkylene" means a saturated divalent hydrocarbon radical having from one to about twelve carbon atoms or a branched saturated divalent hydrocarbon radical having from three to about twelve carbon atoms, for example, methylene, ethylene, propylene, 2- methylpropylene, pentylene, hexylene, and the like.
"Alkyleneoxy" has essentially the meaning given above for alkylene except the alkylene group is terminated by an oxygen atom, for example, -CH2CH2O-, - CH2CH2CH2O-, -CH2CH2CH2CH2O-, -CH2CH(CH3)CH2O-, and the like.
The term "aryl" refers to monovalent unsaturated aromatic carbocyclic radicals having a single ring, such as phenyl, or multiple condensed rings, such as naphthyl or anthryl.
As used herein, the term "oligothiophene" refers to oligomers having at least two thiophene repeat units, linked by a covalent bond at the successive 2 positions.
"(Oligo)thiophene" shall be inclusive of thiophene compounds having one thiophene ring and oligomeric thiophene compounds (oligothiophenes) having two or more thiophene rings.
"Perfluoroalkyl" has essentially the meaning given above for "alkyl" except that all or essentially all of the hydrogen atoms of the alkyl radical are replaced by fluorine atoms and the number of carbon atoms is from 1 to about 12, for example, perfluoropropyl, perfluorobutyl, perfluorooctyl, and the like.
"Perfluoroalkylene" has essentially the meaning given above for "alkylene" except that all or essentially all of the hydrogen atoms of the alkylene radical are replaced by fluorine atoms, for example, perfluoropropylene, perfluorobutylene, perfluorooctylene, and the like.
"Perfluoroalkyloxy" has essentially the meaning given above for "alkyloxy" except that all or essentially all of the hydrogen atoms of the alkyoxy radical are replaced by fluorine atoms and the number of carbon atoms is from 3 to about 12, for example, CF3CF2O-, CF3CF2CF2CF2O-, C3F7CF(CF3)O-, and the like.
"Perfluoroalkyleneoxy" has essentially the meaning given above for "alkyleneoxy" except that all or essentially all of the hydrogen atoms of the alkyleneoxy radical are replaced by fluorine atoms, for example, -CF2O-, -CF2CF2O-, -CF2CF(CF3)O-, and the like. "Perfluoroether" is a saturated, perfluoroinated monovalent alkyl radical having from 2 to about 50 carbon atoms and at least one ether oxygen atom, for example, CF3CF2OCF2-, CF3CF2CF2CF2OCF2CF2-, CF3CF(CF3)O CF2CF2OCF2CF2-, CF3CF(CF3)O-[CF(CF3)-CF2O]n-CF(CF3)-, and the like. "Perfluoroether" is inclusive of perfluoro monoethers and perfluoro poly ethers.
Semiconductor Devices
Semiconductor devices are provided that have a semiconductor layer that contains compound of the formula
wherein each Rf is a perfluoroether group, and n is at least 2, preferably 3 to 6. Rf may be a monoether or a polyether, that is, a monovalent perfluoroalkoxyalkylene group or a monovalent perfluoropolyether group.
The perfluoroheteroalkyl group, Rf, of the fluorinated ether of Formulas I and II preferably corresponds to the formula:
RZ-O-(Rf 2V(Rf 3)- (III) wherein Rf 1 represents a perfluoroalkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, (Rf 2)x represents a perfluoropolyalkyleneoxy group consisting of perfluoroalkyleneoxy groups, Rf2, having 1 to 10 perfluorinated carbon atoms, preferably 1 to 6 carbon atoms, Rf 3 represents a perfluoroalkylene group having 1 to 10 perfluorinated carbon atoms, preferably 1 to 6 carbon atoms, and x is 0 to 25, preferably at least one, more preferably 1 to 4. The perfluoroalkyl and perfluoroalkylene groups in formula (III) may be linear or branched. A typical perfluoroalkyl group is CF3-CF2-CF2-. For example, Rf 3 is -CF2- or -CF(CF3)-.
Examples of perfluoroalkyl groups Rf 1 include CF3-CF2-, CF3-CF(CF3)-, CF3-CF2- CF2-, CF3-, CF3-CF2CF2-CF(CF3)-, CF3-CF2CF(C3F7)-, CF3-CF(C3F7)CF2-, and CF3-CF2- CF2-CF2-.
Examples of perfluoroalkyleneoxy groups of perfluorinated polyalkyleneoxy group Rf 2 include: -CF2-CF2-O-, -CF(CF3)-CF2-O-, -CF2-CF(CF3)-O-, -CF2-CF2-CF2-O-, -CF2-O-, -CF(CF3)-O-, and -CF2-CF2-CF2-CF2-O-.
Examples of perfluoroalkylene groups, Rf 3 include: -CF2-CF2-, -CF(CF3)-CF2-, -CF2-CF(CF3)-, -CF2-CF2-CF2-, -CF2-, -CF(CF3)-, and -CF2-CF2-CF2-CF2-. The perfluoroalkyleneoxy group, Rf2, may be comprised of the same perfluoroalkyleneoxy units or of a mixture of different perfluoroalkylene oxy units. When the perfluoroalkyleneoxy group is composed of different perfluoroalkylene oxy units, they can be present in a random configuration, alternating configuration or they can be present
as blocks. Typical examples of perfluoropolyalkyleneoxy groups include -[CF2-CF2-O]n-; -[CF(CF3KF2-O]n-; -[CF2CF2-O]i-[CF2O]r and -[CF2-CF2-O],-[CF(CF3)-CF2-O]m-; wherein n is an integer of 1 to 25, and i, 1, m and j each are integers of 1 to 25.
In a particular embodiment, the fluorinated polyether, Rf, corresponds to the following formula (IV):
Rf 1-O-[CF(CF3)-CF2O]X-CF(CF3)- (IV) wherein Rf1 represents a perfluorinated alkyl group, for example, a linear or branched perfluorinated alkyl group having 1 to 6 carbon atoms, x is an integer of 0 to 25, preferably at least one, more preferably 1 to 4. A preferred perfluorinated polyether group that corresponds to formula (IV) is CF3-CF(CF3)-O-[CF(CF3)-CF2O]X-CF(CF3)- wherein x is an integer of 1 to 4. This perfluoropolyether can be derived from an oligomerization of hexafluoropropylene oxide.
Preferred perfluoroether groups, Rf, are dimers, trimers and tetramers derived from the hexafluoropropylene oxide (HFPO) and correspond to the structures: F(CFCF2O)1-4CF- CF3 CF3
The corresponding acids, acid halides and esters may be prepared from the oligomerization of hexafluoropropylene oxide, or the oxidative oligomerization of hexafluoropropylene, such as is known in the art. Many of these compounds are commercially available from Matrix Scientific, Columbia, SC. Compounds according to formula (IV) can for example be obtained by oligomerization of hexafluoropropylene oxide, which results in a perfluoropolyether carbonyl fluoride. This carbonyl fluoride may be converted into an acid, or ester by reactions well known to those skilled in the art. The carbonyl fluoride or acyl fluoride, acid, or ester derived therefrom may then be reacted further to introduce the desired perfluoroether groups into the oligothiophene compounds according to known acylation procedures. For example, U.S. 6,127,498 or U.S. 3,536,710 describe suitable methods to produce compounds according to formula (IV) having desired acyl moieties.
Further details concerning the materials and procedures for the preparation of perfluorinated polyethers can be found in, for example, U.S. Pat. Nos. 3,242,218 (Miller); 3,322,826 (Moore); 3,250,808 (Moore et al.); 3,274,239 (Selman); 3,293,306 (Le Bleu et al.); 3,810,874 (Mitsch et al.); 3,544,537 (Brace); 3,553,179 (Bartlett); 3,864,318
(Caporiccio et al.); 4,321,404 (Williams et al), 4,647,413 (Savu); 4,818,801 (Rice et al.); 4,472,480 (Olson); 4,567,073 (Larson et al.); U.S. Pat. No. 4,830,910 (Larson); US 5362919 (Costello) US 5578278 (Fall) and 5,306,758 (Pellerite). See also Patricia M. Savu, Fluorinated Higher Carboxylic Acids, 11 Kirk-Othmer Encyclopedia of Chemical Technology 551-58 (4th ed. 1994).
Perfluoroether acyl (oligo)thiophene compounds of Formula I, where Y is not a perfluoroether acyl group, may be prepared as follows. Thiophene (Y=H) may be treated with an alkyl lithium reagent, followed by acylation with a perfluoroether ester (in presence of a Lewis acid catalyst such as BF3-Et2O) to produce the mono perfluoroether acyl compound. The corresponding 5 -alkyl or 5-aryl compounds (Y= alkyl or aryl) may be prepared by an analogous route starting from 2-alkyl or 2-aryl thiophene (such as are known in the art), followed by acylation and optional bromination. The corresponding 2- bromo-5-perfluoroether acyl compound may be prepared by monoacylation of 2,5- dibromothiophene to directly produce the 2-bromo-5-perfluoroether acyl compound.
Higher thiophene compounds, where Y is H, halogen, alkyl or aryl may be prepared by Stille coupling of a thienyl stannane with an α-bromo-ω-perfluoroether acyl thiophene according to the following general scheme:
Preferred α,ω-bis-perfmoroether acyl oligothiophene compounds of Formula II may be prepared according to Reaction Scheme A by a Stille coupling reaction. Generally, the oligothiophenes may be prepared by reacting a
bis(trialkylstannyl)thiophene (such as a 2,5-bis(trialkylstannyl)thiophene or a 5,5'- bis(trialkylstannyl)bithiophene) with a 2-perfluoroether acyl 5-halothiophene (or a 5- perfluoroether acyl 5'-halobithiophene) in the presence of a palladium catalyst.
A 2-halo-5-perfluoroetheracyl thiophene (such compounds of formulas VI) or a 5- halo-5'-perfluoroetheracylbithiophene (such compounds of formulas X) can be reacted with a bis(trialkylstannyl) compound (that is, Formula V or VIII, where R is an alkyl group) to form a α,ω-bis(2-perfluoroetheracyl oligothiophene (that is, Formula VII, IX, XI or XII). The Stille coupling reaction may be performed as outlined in Farina V. and Krishnamurthy, V. in Organic Reactions; L.A. Paquette, Ed., John Wiley and Sons., 1997; vol. 50, pp. 1-652. The reaction products may be purified to a semiconductor grade material by any known process such as by vacuum sublimation.
Reaction Scheme A
VIII VI IX
The bis-trialkylstannyl thiophene compounds of formulas V and VIII are known. Reference may be made to Y. Wei et al. Chem. Mater. Vol. 8, 1996, pp.2659-2666.
The monoacyl compound of formula VI may be made by treatment of 2,5- dihalothiophene with an alkyl lithium compound, to produce the 2-bromo-5-lithio thiophene, followed by reaction with a perfluorinated ether ester (or equivalent) in the presence of boron trifluoride etherate. This method yields the desired product V in high yields, and has proven superior to other known methods, such as formation of the cuprate, followed by reaction with a perfluorinated acyl compound.
The monoacyl bithiophene compound X may be prepared by a two-step synthesis comprising first reacting 5-lithio-2,2'-bithiophene (generated in situ) with a perfluorinated ether ester (or equivalent) in the presence of boron trifluoride etherate), followed by bromination, such as by N-bromosuccinimide.
With reference to compounds VI and X, 5-halo-5'-perfluoroether acyl thiophene compounds are useful in the preparation of the bis-perfluoroether thiophene compounds of the present invention. Such novel compounds are of the general formula:
where Y is H, a halogen, an aryl or an alkyl group, Rf is a perfluoroether group and p is 1 to 6 Compounds where p is 2 or greater may be prepared by a Stille coupling reaction of a compound of formula VI or X with a mono-trialkylstannyl thiophene or a mono-
trialkylstannyl bithiophene, followed by halogenation of the ω-5 position of the terminal thiophene ring.
The bithiophene compound of formula XIII may be prepared by coupling of the 5- bromo-2-thienyl magnesium bromide and a perfluoroether acid halide according to the procedure described in Portnoy, J. Org. Chem, vol. 32, 1967, pp 233-4. The Ullman coupling reactions may also prove useful.
Asymmetric α,ω-bis-perfluoroether acyl oligothiophenes (that is, a oligothiophenes with different perfluoroether acyl groups can be prepared, for example, through using a mixture of compounds of Formulas VI or X having different Rf groups, although a mixture of products will result. With respect to each of the reaction schemes, the preferred bromo-substituted thiophenes are illustrated, but other halides may also be used.
Other synthetic approaches can be used to prepare α,ω-bis-perfluoroether acyl oligothiophene compounds. For example, the thiophene-2-aldehyde may be reacted with a perfluoroether organometallic compounds (such as Rf-Li, generated in situ) to produce the alcohol shown. This may be brominated at the 5 -position, followed by oxidation of the hydroxyl group to the ketone. Reference may be made to the general methods described in U.S. 6,608,323 and 6,585,914 (Marks et al.).
VI
The compounds of the invention may be used as a n-channel semiconductor. The semiconductor layer that contains a α,ω-bis-perfluoroether acyl oligothiophene compound can be included in any type of semiconductor device. Semiconductor devices have been described, for example, by S. M. Sze in Physics of Semiconductor Devices. 2nd edition, John Wiley and Sons, New York (1981). Such devices may include rectifiers, transistors (of which there are many types, including p-n-p, n-p-n, and thin-film transistors), photoconductors, current limiters, thermistors, p-n junctions, field-effect diodes, Schottky diodes, and the like.
Semiconductor devices can include components such as transistors, arrays of transistors, diodes, capacitors, embedded capacitors, and resistors that are used to form circuits. Semiconductor devices also can include arrays of circuits that perform an electronic function. Examples of these arrays, or integrated circuits, are inverters, oscillators, shift registers, and logic. Applications of these semiconductor devices and arrays include radio frequency identification devices (RPIDs), smart cards, displays backplanes, sensors, memory devices, and the like.
Each semiconductor device contains a semiconductor layer with a compound according to Formulas I or II. The semiconductor layer can be combined with a conductive layer, a dielectric layer, or a combination thereof to form the semiconductor device. Semiconductor devices can be prepared or manufactured by known methods such as, for example, those described by Peter Van Zant in Microchip Fabrication, Fourth Edition, McGraw-Hill, New York (2000).
Some of the semiconductor devices are organic thin-film transistors. One embodiment of an organic thin-film transistor 10 is shown in Figure 1 a. The organic thin- film transistor (OTFT) 10 includes an optional substrate 12, a gate electrode 14 disposed on the optional substrate 12, a gate dielectric material 16 disposed on the gate electrode 14, an optional surface treatment layer 18 disposed on the gate dielectric layer 16, a source electrode 22, a drain electrode 24, and a semiconductor layer 20 that is in contact with both the source electrode 22 and the drain electrode 24. The source electrode 22 and the drain electrode 24 are separated from each other in an area on the surface of the semiconductor layer 20 (that is, the source electrode 22 does not contact the drain electrode 24). The portion of the semiconductor layer that is positioned between the source electrode and the drain electrode is referred to as the channel 21. The channel is positioned over the gate electrode 14, the gate dielectric layer 16, and the optional surface treatment layer 18. The semiconductor layer 20 contacts the gate dielectric layer 16 or the surface treatment layer 18.
A second embodiment of an organic thin-film transistor is shown in Figure Ib. This OTFT 100 includes a gate electrode 14 disposed on an optional substrate 12, a gate dielectric layer 16 disposed on the gate electrode 14, an optional surface treatment layer 18 disposed on the gate dielectric layer 16, a semiconductor layer 20, and a source electrode 22 and a drain electrode 24 disposed on the semiconductor layer 20. In this embodiment,
the semiconductor layer 20 is between the gate dielectric layer 16 and both the source electrode 22 and the drain electrode 24. The semiconductor layer 20 can contact the gate dielectric layer 16 or the optional surface treatment layer 18. The source electrode 22 and the drain electrode 24 are separated from each other (that is, the source electrode 22 does not contact the drain electrode 24) in an area on the surface of the semiconductor layer 20. The channel 21 is the portion of the semiconductor layer that is positioned between the source electrode 22 and the drain electrode 24. The channel 21 is positioned over the gate electrode 14, the gate dielectric layer 16, and the optional surface treatment layer 18.
In operation of the semiconductor device configurations shown in Figures Ia and Ib, voltage can be applied to the drain electrode 24. However, no charge (that is, current) is passed to the source electrode 22 unless positive voltage is also applied to the gate electrode 14, relative to the source electrode 22. That is, unless voltage is applied to the gate electrode 14, the channel 21 in the semiconductor layer 20 remains in a non- conductive state. Upon application of voltage to the gate electrode 14, the channel 21 becomes conductive and charge flows through the channel 21 from the source electrode 22 to the drain electrode 24.
A substrate 12 often supports the OTFT during manufacturing, testing, and/or use. Optionally, the substrate can provide an electrical function for the OTFT. For example, the backside of the substrate can provide electrical contact. Useful substrate materials include, but are not limited to, inorganic glasses, ceramic materials, polymeric materials, filled polymeric materials (for example, fiber-reinforced polymeric materials), metals, paper, woven or non-woven cloth, coated or uncoated metallic foils, or a combination thereof. Suitable polymeric substrates include acrylics, epoxies, polyamides, polycarbonates, polyimides, polyketones, polynorbornenes, polyphenyleneoxides, poly(ethylene naphthalate), poly(ethylene terephthalate), poly(phenylene sulfide), poly(ether ether ketones) such as poly(oxy-l,4-phenyleneoxy-l,4-phenylenecarbonyl-l,4- phenylene), and the like.
The gate electrode 14 can include one or more layers of a conductive material. For example, the gate electrode can include a doped silicon material, a metal, an alloy, a conductive polymer, or a combination thereof. Suitable metals and alloys include, but are not limited to, aluminum, chromium, gold, silver, nickel, palladium, platinum, tantalum, titanium, indium tin oxide (ITO) or a combination thereof. Exemplary conductive
polymers include, but are not limited to, polyaniline or poly(3,4- ethylenedioxythiophene)/poly(styrene sulfonate). In some organic thin film transistors, the same material can provide both the gate electrode function and the support function of the substrate. For example, doped silicon can function as both the gate electrode and as a substrate.
The gate dielectric layer 16 is disposed on the gate electrode 14. This gate dielectric layer 16 electrically insulates the gate electrode 14 from the balance of the OTFT device. Useful materials for the gate dielectric include, for example, an inorganic dielectric material, a polymeric dielectric material, or a combination thereof. The gate dielectric can be a single layer or multiple layers of suitable materials. Each layer in a single or multilayer dielectric can include one or more dielectric materials.
Exemplary inorganic dielectric materials include strontiates, tantalates, titanates, zirconates, aluminum oxides, silicon oxides, tantalum oxides, titanium oxides, silicon nitrides, barium titanate, barium strontium titanate, barium zirconate titanate, zinc selenide, zinc sulfide, hafnium oxides, and the like. In addition, alloys, combinations, and multiple layers of these materials can be used for the gate dielectric layer 16.
Exemplary polymeric dielectric materials include polyimides, parylene C, crosslinked benzocyclobutene, cyanoethylpullulan, polyvinyl alcohol, and the like. See, for example, CD. Sheraw et al., "Spin-on polymer gate dielectric for high performance organic thin film transistors", Materials Research Society Symposium Proceedings, vol. 558, pages 403-408 (2000), Materials Research Society, Warrendale, PA, USA; and U.S. Patent No. 5,347,144 (Gamier).
Other exemplary organic polymeric dielectrics include cyano-functional polymers such as cyano-functional styrenic copolymers as disclosed in U.S. Patent Application Serial No. 10/434,377, filed May 8, 2003. Some of these polymeric materials can be coated from solution, can be crosslinked, can be photo-patterned, can have high thermal stability (for example, stable up to a temperature of about 250 0C), can have a low processing temperature (for example, less than about 150 0C or less than about 100 0C), can be compatible with flexible substrates, or combinations thereof. Exemplary cyano-functional polymers that can be used as organic dielectric materials include, but are not limited to, styrene maleic anhydride copolymers modified by adding a methacrylate functional group for crosslinking purposes and by attaching cyano-
functional groups; the reaction product of bis(2-cyanoethyl)acrylamide with an acrylated polystyrene macromer; polymers formed from 4-vinylbenzylcyanide; polymers formed from 4-(2,2'-dicyanopropyl)styrene; polymers formed from 4-(l,l ',2- tricyanoethyl)styrene; and polymers formed from 4-(bis-(cyanoethyl)aminoethyl)styrene; and a copolymer formed from 4-vinylbenzylcyanide and 4-vinylbenzylacrylate.
The organic thin film transistors can include an optional surface treatment layer 18 disposed between the gate dielectric layer 16 and at least a portion of the organic semiconductor layer 20. In some embodiments, the optional surface treatment layer 18 serves as an interface between the gate dielectric layer and the semiconductor layer. The surface treatment layer can be a self-assembled monolayer or a polymeric material.
Suitable self-assembled monolayer surface treatment layers are disclosed, for example, in U.S. Patent No. 6,433,359 Bl (Kelley et al.). Exemplary self-assembled monolayers can be formed from l-phosphono-2-ethylhexane, l-phosphono-2,4,4- trimethylpentane, l-phosphono-3,5,5-trimethylhexane, 1 -phosphonoctane, 1- phosphonohexane, 1-phosphonohexadecane, l-phosphono-3,7,11,5- tetramethylhexadecane, and the like.
Useful polymers and copolymers for a surface treatment layer are usually non- polar, glassy solids at room temperature. The polymeric materials in this layer typically have glass transition temperature (Tg) measured in the bulk of at least 25 °C, of at least 50 °C, or of at least 100 0C. Suitable polymeric surface treatment layers are described, for example, in U.S. Patent Application Publication 2003/0102471 Al (Kelley et al.) and U.S. Patent No. 6,617,609 (Kelley et al.)
Exemplary polymeric surface treatment layers can contain polystyrene, polyfluorene, polynorbornene, poly(l-hexene), poly(methyl methacrylate), poly(acenaphthylene), poly(vinylnaphthalene), poly(butadiene), and polyvinyl acetate). Other exemplary polymeric surface treatment layers can contain polymers or copolymers derived from α-methylstyrene, 4-tert-butylstyrene, 2-methylstyrene, 3-methylstyrene, 4- methylstyrene, 4-(phosphonomethyl)styrene, divinyl benzene, and combinations thereof. Examples of still other useful polymeric materials for the surface treatment layer include poly(dimethylsiloxane), poly(dimethylsiloxane-co-diphenylsiloxane), poly(methylphenylsiloxane-co-diphenylsiloxane), poly(dimethylsiloxane-co- methylphenylsiloxane), and the like.
The surface treatment layer often has a maximum thickness less than 400 Angstroms (A). For example, the surface treatment layer can be less than 200 A, less than 100 A, or less than 50 A. The surface treatment layer generally has a thickness of at least about 5 A, at least about 10 A, or at least 20 A. The thickness can be determined through known methods such as ellipsometry.
The source electrode 22 and drain electrode 24 can be metals, alloys, metallic compounds, conductive metal oxides, conductive ceramics, conductive dispersions, and conductive polymers, including, for example, gold, silver, nickel, chromium, barium, platinum, palladium, aluminum, calcium, titanium, indium tin oxide (ITO), fluorine tin oxide (FTO), antimony tin oxide (ATO), indium zinc oxide (IZO), poly(3,4- ethylenedioxythiophene)/poly(styrene sulfonate), polyaniline, other conducting polymers, alloys thereof, combinations thereof, and multiple layers thereof. Some of these materials are appropriate for use with n-type semiconductor materials and others are appropriate for use with p-type semiconductor materials, as is known in the art. The thin film electrodes (for example, the gate electrode, the source electrode, and the drain electrode) can be provided by any means known in the art such as physical vapor deposition (for example, thermal evaporation or sputtering), ink jet printing, or the like. The patterning of these electrodes can be accomplished by known methods such as shadow masking, additive photolithography, subtractive photolithography, printing, microcontact printing, and pattern coating.
The semiconductor devices that contain the perfluoroether acyl oligothiophene compounds tend to have performance characteristics such as charge-carrier mobility and current on/of ratio that are comparable to known organic semiconductor devices such as those that contain pentacene. For example, semiconductor devices can be prepared that have an n-channel mobility of about 1 cm /volt-sec and on-off ratio greater than about 10 . In another aspect, a method of preparing a semiconductor device is provided. The method involves preparing a semiconductor layer that contains a perfluoroether acyl oligothiophene compound of Formulas I or II, where n is preferably 3 to 6. The semiconductor layer is usually formed using a vapor deposition process. In some exemplary methods of preparing a semiconductor device, the method involves preparing a semiconductor layer that contains a perfluoroether acyl oligothiophene compound of Formulas I or II; and depositing a dielectric layer, a
conductive layer, or a combination thereof adjacent to the semiconductor layer. As used herein, the term "adjacent" refers to a first layer that is positioned near a second layer. The first layer often contacts the second layer but another layer could be positioned between the first and second layer. No specific order of preparing or depositing is necessary; however, the semiconductor layer is often prepared on the surface of another layer such as the dielectric layer, conductive layer, or a combination thereof.
One exemplary method of preparing a semiconductor device provides an organic thin film transistor. The method includes preparing a semiconductor layer that contains a perfluoroether acyl oligothiophene compound of Formulas I or II; positioning a source electrode and a drain electrode on a surface of the semiconductor layer such that the source electrode and the drain electrode are separated in an area on the surface of the semiconductor layer (that is, the source electrode does not contact the drain electrode). The method can further include providing a gate dielectric layer, a gate electrode, and an optional surface treatment layer. More specifically, an organic thin film transistor can be prepared by providing a gate electrode; depositing a gate dielectric layer on a surface of the gate electrode; preparing a semiconductor layer adjacent to the gate dielectric layer (that is, the gate dielectric is positioned between the gate electrode and the semiconducting layer); and positioning a source electrode and a drain electrode on a surface of the semiconductor layer that is opposite the gate dielectric layer. The source electrode and the drain electrode are separated from each other in an area on the surface of the semiconductor layer.
In one embodiment of this method, the various layers of the semiconductor device are arranged in the following order: gate electrode; gate dielectric layer; semiconductor layer; and a layer containing a source electrode and a drain electrode. In another embodiment, the various layers of the semiconductor device are arranged in the following order: gate electrode, gate dielectric layer, surface treatment layer, semiconductor layer, and a layer containing a source electrode and a drain electrode. The source electrode does not contact the drain electrode in these embodiments. That is, the source electrode and the drain electrode are separated from each other in an area on the surface of the semiconductor device. One surface of the semiconductor layer contacts both the source electrode and the drain electrode while the opposite surface of the semiconductor layer contacts the gate dielectric layer or the surface treatment layer.
The organic thin film transistor exemplified in Figure Ib can be prepared by providing a substrate, depositing a gate electrode on the substrate, depositing a gate dielectric layer on a surface of the gate electrode such that the gate electrode is positioned between the substrate and the gate dielectric layer; applying a surface treatment layer to a surface of the gate dielectric layer opposite the gate electrode; preparing a semiconductor layer on a surface of the surface treatment layer opposite the gate dielectric layer; and positioning a source electrode and a drain electrode on a surface of the semiconductor layer that is opposite the polymeric treatment layer. The source electrode and the drain electrode are separated from each other in an area on the surface of the semiconductor layer. The area of separation between the source electrode and the drain electrode can define a channel in the semiconductor layer.
Another organic thin film transistor can be prepared by providing a gate electrode; depositing a gate dielectric layer on a surface of the gate electrode; positioning a source electrode and a drain electrode adjacent to the gate dielectric material such that the source electrode and the drain electrode are separated from each other in an area over the gate dielectric layer; preparing a semiconductor layer that is deposited on the source electrode, drain electrode, and in the area between the source electrode and the drain electrode. The semiconductor layer contacts both the source electrode and the drain electrode. The portion of the semiconductor layer that is positioned in the area between the source electrode and the drain electrode defines the channel.
In one embodiment of this method, the various layers of the semiconductor device are arranged in the following order: gate electrode; gate dielectric layer; a layer containing a source electrode and a drain electrode; and a semiconductor layer. In another embodiment, the various layers of the semiconductor device are arranged in the following order: gate electrode; gate dielectric layer; surface treatment layer; a layer containing a source electrode and a drain electrode; and semiconductor layer. The source electrode does not contact the drain electrode in these embodiments. A portion of the semiconductor layer can extend between the source electrode and the drain electrode. The organic thin film transistor exemplified in Figure Ia can be prepared by providing a substrate, depositing a gate electrode on the substrate, depositing a gate dielectric layer on a surface of the gate electrode such that the gate electrode is positioned between the substrate and the gate dielectric layer; applying a surface treatment layer to a
surface of the gate dielectric layer opposite the gate electrode; positioning a source electrode and a drain electrode on a surface of the polymeric treatment layer such that the two electrodes are separated from each other in an area; preparing a semiconductor layer on the source electrode, drain electrode, and in the area between the source electrode and the drain electrode. The semiconductor layer contacts both the source electrode and the drain electrode. The portion of the semiconductor layer that is positioned in the area between the source electrode and the drain electrode defines a channel in the semiconductor layer.
The organic thin film transistors or other semiconductor devices such as integrated circuits can be prepared using flexible, repositionable polymeric aperture masks. The technique involve sequentially depositing material through a number of polymeric aperture masks formed with patterns that define layers, or portions of layers, of the semiconductor device. The use of such polymeric aperture masks are further described in U.S. Patent Publication Nos. 2003/0094959-A1, 2003/0150384-A1, 2003/0152691-A1, and 2003/0151118-Al.
Repositionable polymeric aperture masks often have a thickness of 5 to 50 micrometers or 15 to 35 micrometers. The various deposition apertures in the aperture masks usually have widths less than 1000 micrometers, less than 50 micrometers, less than 20 micrometers, less than 10 micrometers, or even less than 5 micrometers. Apertures of these sizes are particularly useful in creating small circuit elements for integrated circuits. Moreover, one or more gaps between deposition apertures are typically less than 1000 micrometers, less than 50 micrometers, less than 20 micrometers, or less than 10 micrometers, which is also useful in creating small circuit elements. The aperture masks can have a pattern with a width greater than 1 centimeter, 25 centimeters, 100 centimeters, or even 500 centimeters. Patterns having these widths can be useful in creating various circuits over a larger surface area.
Various laser ablation techniques may be used to facilitate the creation of polymeric aperture masks having patterns of deposition apertures. In addition, stretching techniques and other techniques may be used to facilitate alignment of flexible polymeric aperture masks. Furthermore, methods of controlling sag in aperture masks may be used which can be particularly useful in using masks that include a pattern that extends over a large width.
Other methods known in the art can be used to prepare the semiconductor devices. These methods include, for example, metal shadow masks; photolithography and/or etching; and printing methods such as inkjet, screen-printing, gravure printing, and the like. In some methods that involve the use of aperture masks, semiconductor devices
(for example, integrated circuits) can be created solely using aperture mask deposition techniques, without requiring any of the etching or photolithography steps typically used to form such devices. The techniques can be particularly useful in creating circuit elements for electronic displays such as liquid crystal displays and low-cost integrated circuits such as radio frequency identification (RPID) circuits. In addition, such techniques can be advantageous in the fabrication of integrated circuits incorporating organic semiconductors, which typically are not compatible with photolithography or other wet chemical processes.
EXAMPLES
Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. All reactions were carried out under nitrogen. Melting points were determined by DSC analyses under N2 at a ramp rate of 20 °C/min and are reported as the range between the onset temperature and the peak maximum. Combustion analyses were run using a LECO 932 CHNS elemental analyzer (LECO Corporation, St. Joseph, MI). Infrared spectra were recorded using pellets pressed with KBr. Positive ion mass spectrometry was done using an Applied Biosystems Inc. DE/STR MALDI/TOF mass spectrometer (Applied Biosystems, Inc., Foster City, CA). Dilute CHCl3 solutions of the samples were deposited directly on the probe tip without a matrix. 1H and 19F NMR spectra were collected in d6-acetone at 200 MHz and 188 MHz, respectively, unless otherwise indicated. Internal tetramethylsilane and fluorotrichloromethane were referenced to 0.0 ppm. Silica gel for column chromatography was purchased from Aldrich (Milwaukee, WI; Merck, grade 9385, 230-400 mesh, 6θA). Tetrahydrofuran (THF) and diethyl ether (Et2O) were distilled from sodium/benzophenone ketyl. N,N-dimethylformamide (DMF) was vacuum distilled under nitrogen from MgSO4 or purchases as anhydrous grade from
Aldrich. All other solvents were used as obtained. Bithiophene, 2,5-dibromothiophene, 3- bromothiophene, boron trifluoride diethyl etherate, aluminum trichloride, /-z-butyl lithium (1.6 M or 2.5 M in hexanes), iV-bromosuccimide (NBS), and dimethylamine borane were purchased from Aldrich. NBS was recrystallized from hot water and dried under vacuum prior to use. Perfluoro(2,5-dimethyl-3,6-dioxanonanoic) acid methyl ester (HFPO trimer carbomethoxylate), methyl 3,6-dioxadecanoate, and methyl 3,6,9-trioxadecanoate were purchased from Matrix Scientific (Columbia, SC) and used as received. Tetrakis(triphenylphosphine)palladium (0) was purchased from Strem Chemicals, Newburyport, MA. 5,5'-bis(tri-π-butylstannyl)-2,2'-bithiophene and 5,5'-bis(tri-«- butylstannyl)thiophene were synthesized using the procedure published by Y. Wei, Y. Yand, and J.-M Yeh, Chem. Mater. , 8, 2659-2666 (1996).
Example 1
5-Perfluoro(3 ,6,9-trioxadecanoyl)-2,2 '-bithiophene
A hexanes solution of BuLi (10.18 rnL, 16.3 mmol) was added drop wise to a cold (-70 0C) THF solution (250 mL) of bithiophene (2.71 g, 16.3 mmol). After 30 min, CF3(OC2F4)2OCF2CO2Me (7.66 g , 16.4 mmol) and BF3»OEt2 (2.5 mL, 19.6 mmol, 1.2 eq) were added sequentially and the mixture stirred at -70 0C for 90 min. A few mL of saturated NH4Cl (aq) were charged, the mixture was warmed to room temperature, and the volatile materials removed under reduced pressure. Et2O (400 mL) and brine (250 mL) were charged and the reaction was stirred vigorously.
The mixture was filtered through a Celite pad and the amber organic washed with 2 x 100 mL brine, dried with MgSO4, and filtered. The solvent was stripped and the material adsorbed onto silica gel. The crude product was purified by column chromatography (hexanes/EtOAc, 0%-3%) to aford 6.38 g (70%) of yellow product. Mp (ΔH): 50-53 0C (51 J/g). IR: 1684 (vco), 1505 w, 1450 m, 1423w, 1229 s, 1193 s, 1139 s, 1103 s, 1077 s, 906 m, 869 m, 842 m, 803 m, 741 m, 706 s, 682 m, 619 w, 546 w, 522 w, 508 w, 453 w cm"1. 1H NMR: δ 7.22 (dd, J= 5.1 Hz, 3.8 Hz, 5'-H), 7.56 (d, J= 4.3 Hz, 3-
H), 7.67 (dd, J= 3.7 Hz, 1.1 Hz, 4'-H), 7.73 (dd5 J= 5.1 Hz, 1.1 Hz, 3'-H), 8.01 (dt, J= 4.3 Hz, 1.7 Hz, 4-H). 19F NMR: δ -55.03 (t, J= 9.0 Hz, CF3), -74.43 (m, 8-lines, COCF2), -87.50 (m, 5 lines, CF2), -88.16 (br, 2 CF2 groups), -90.19 (q, J= 9.4 Hz, CF2OCF3). Anal. Calcd for C15H5Fi3O4S2: C, 32.15; H, 0.90; S, 11.45. Found: C, 32.2; H, 0.9; S, 11.6.
Example 2
5-Perfluoro(3 ,6-dioxadecanoyl)-2,2 '-bithiophene
This compound was prepared analogously to Example 1. A reaction between BuLi (36.75 rnL, 58.8 mmol) and bithiophene (9.75 g, 58.6 mmol) in cold THF (250 mL, -70 °C) was stirred for 30 min, followed by a sequential addition of C4F9OC2F4OCF2CO2Me (30.2 g , 65.7 mmol) and BF3OEt2 (9.0 mL, 71 mmol).
The material was purified by chromatography to afford 18.7 g (54%) of yellow product. Mp (ΔH):50-53 0C (45 J/g). IR: 1666 m (vco), 1504 w, 1448 m, 1309 m, 1233 s, 1202 s, 1153 s, 1081 m, 1027 m, 993 m, 851 w, 837 w, 802 m5 763 w, 752 w, 802 m, 763 w, 752 w, 721 m, 710 m, 654 w, 616 w, 532 w, 460 w cm"1. 1H NMR: δ 7.20 (dd, J= 5.17 Hz, 3.8 Hz, 5'-H), 7.53 (d, J= 4 Hz, 3-H), 7.64 (dd, J= 4 Hz, 1 Hz, 4'-H), 7.69 (dd, J= 5.1 Hz, 1.1 Hz, 3'-H), 7.98 (dt, J= 4.2 Hz, 1.6 Hz, 4-H). 19F NMR: δ -74.46 (t, J= 12.2 Hz, CF3), -80.88 (br, COCF2O), -83.08 (br, OCF2CF2O), -87.60 (T, J=12.0 Hz, - OCF2CF2O), -88.05 (T, J= 12.7 Hz, OCF2C3F7), -126.14 (m, CF2CF2CF2CF3). Anal. Calcd for C16H5F15O3S2: C, 32.33; H, 0.85; S, 10.79. Found: C, 32.1; H, 0.8; S, 10.9.
Example 3
5-Perfluoro(2,5-dimethyl-3,6-dioxanonanoyl)-2,2'-bithiophene O
H. ik CF(CF3)OCF2CF(CF3)OC3F7
This compound was prepared analogously to Example 1. Reaction between bithiophene (7.90 g, 47.5 mmol), BuLi (47.6 mmol), HFPO trimer carbomethoxylate (26.7
g, 52.2 mmol)5 and BF3OEt2 (7.0 niL, 55 mmol) in 250 mL of cold THF yielded 24.8 g (81%) of product. Mp (ΔH):37^0°C 37 (J/g). IR: 1666 s (v∞), 1504 w, 1449 S5 1310 s, 1233 s, 1202 vs, 1153 s, 1081 m,1027 m, 993 s, 897 w, 850 m, 837 m, 802 s, 763 m. 752 m, 721 m, 710 S5 654 m, 616 m,532 m, 456 w cm"1. 1H NMR: δ 7.23 (dd, J= 4.0 Hz5 5.0 Hz, 5'-H), 7.59 (d, J= 4.4 Hz,3-H), 7.70 (dd, J = 3.8 Hz5 1.2 Hz5 4'-H)5 7.74 (dd, J= 5.2 Hz5 1.2 Hz, 3'-H), 8.16 (T, J =4.0 Hz, 4-H). 19F NMR: δ -76.8 to -82.1 (m, 4 F OCF2CF(CF3)OCF2-), -79.8 (s, 3 F, CF2CFCF3), -81.1 (s, 6 F, COCFCF3 and CF2CF3), - 129.2 (br m, 1 F, COCFCF3), -129.2 (s, 2 F5 OCF2CF2CF3), -144.6 (br m, 1 F, OCF2CFCF3O). A number of the resonances in the 19F NMR data are observed as pairs due to the asymmetric centers of the fluorinated group. Anal, calcd for C17H5F17O3S2: C, 31.69; H5 0.78; S5 9.95. Found: C5 31.3; H5 0.8; S, 9.9.
Example 4
5-Bromo-5 '-perfluoro(3,6,9-trioxadecanoyl)-252 '-bithiophene.
NBS (2.50 g, 13.32 mmol) was added to a stirred mixture of DMF (250 mL) and 5-perfluoro(3,659-trioxadecanoyl)-252 '-bithiophene (6.22 g5 11.1 mmol) that was covered with aluminum foil. The solution was stirred overnight, poured into 500 mL of brine, and extracted with Et2O (500 mL) and hexanes (250 mL). The yellow extract was separated, washed with 100 mL brine, 100 mL water, dried with MgSO4, and filtered.
Concentration of the filtrate followed by cooling at —15 °C overnight afforded 5.32 g (75%) of bright yellow product. Mp (ΔH): 78-81 0C (47 J/g). IR: 1677 s (vco), 1509 w5 1452 m5 1421 m, 1231 s, 1191 s, 1153 s, 1104 s, 1076 s, 906 m, 891 m, 861 m, 837 w, 791 m, 740 m, 714 m, 683 m, 648 w, 545 w, 523 W5 510 W5 457 w cm"1. 1H NMR: δ 7.30 (d, J = 4.0 Hz5 3'-H), 7.51 (d, J= 4.0 Hz5 4-H), 7.56 (d, J= 4.3 Hz, 3-H)5 8.02 (dt, J= 4.3 Hz5 1.4 Hz5 4'-H). 19F NMR: δ -55.03 (t, J= 9.2 Hz5 CF3), -74.49 (m, COCF2), -87.49 (m, CF2), -88.15 (br 2 CF2 groups), -90.19 (q, J= 8.1Hz, CF2OCF3). Anal. Calcd for C15H4BrF13O4S2: C5 28.19; H5 0.63; S5 10.03. Found:C5 28.2; H5 0.4; S5 10.1.
Example 5
5-Bromo-5'-perfluoro(3,6-dioxadecanoyl)-2,2'-bithiophene O
Br. ιΛ CF2O(CF2CF2O)C4F9
A DMF solution (200 niL) of 5-perfiuoro(3,6-dioxadecanoyl)-2,2'-bithiophene (17.20 g, 28.94 mmol) was charged with NBS (6.70 g, 37.6 mrnol) and stirred overnight covered with foil. Orange crystals of the product precipitated from the solution. Et2O (200 mL) and brine (200 niL) were added to the reaction and the solution washed in a separatory funnel. The organic layer was separated and washed with 3 x 200 mL of brine. The organic was dried with MgSO4, filtered, and the volatile materials removed under reduced pressure to afford 18.63 g (96%) of yellow product. The crude product was clean by NMR spectroscopy and used directly in further reactions. Mp (ΔH): 86-89 0C (49 J/g); an endothermic transition at 82 0C was present in the first scan only. IR: 1671 s, 1508 w, 1446 s, 1420 w, 1337 w, 1312 m, 1290 w, 1219 s, 1192 s, 1144 s, 1114 m, 1082 m, 975 w, 954 w, 901 w, 891 w, 860 w, 821 w, 788 m, 736 w, 714 w, 693 w, 684 w, 649 w, 597 w, 543 w, 509 w, 457 w, 409 w cm"1. 1HNMR: δ 7.30 (d, J= 4.0 Hz, 3'- H), 7.51 (d, J= 4.0 Hz, 4-H), 7.56 (d, J= 4.3 Hz, 3-H), 8.02 (dt, J= 4.3 Hz, 1.6 Hz, 4'H). 19F NMR: δ -74.20 (t, J= 12 Hz, CF3), -80.76 (m, COCF2O), -82.99 (m, OCF2CF2O), -87.52 (m, OCF2CF2O), -87.97, (m, OCF2C3F7), -126.09 (br m, OCF2C2F4CF3).
Example 6
5-Bromo-5r-perfluoro(2,5-dimethyl-3,6-dioxanonanoyl)-2,2'-bithiophene
This compound was prepared using an identical procedure to that used in Example 5 to afford 16.1 g (94%) of yellow product. Mp (ΔH):51-55 0C (34 J/g). IR: 1661 s (vco), 1505 w, 1448 s, 1421 m, 1299 s, 1237 vs, 1203 s, 1149 s, 1081 s, 1029 s, 994 s, 884 m, 835 m, 814 m, 790 s, 752 w, 743w, 723 m, 705 m, 651 m, 615 m, 532 m, 458 m cm"1. ]H NMR: δ 7.30 (d, J= 3.8 Hz, 3'- H), 7.53 (d, J= 4.0 Hz, 4-H), 7.57 (d, J= 4,4 Hz, 3-H),
8.15 ('t\ J= 4.0 Hz, 4'-H). 19F NMR: δ -76.7 to -82.1 (m, 4 F, 0CF2), -79.4 (s, 3 F, CF3), -81.1 (s, 6 F, CF3), -129.0 (m, 1 F, CF), -129.2 (m, 2 F, CF2CF2CF3), -144.7 (m, 1 F, CF). A number of the resonances in the 19F data are observed as pairs due to the two asymmetric centers of the fluorinated end group. Anal. Calcd for C17H4BrF17O3S2: C5 28.23; H, 0.56; S, 8.87. Found: 28.6; H, 1.1; 9.1.
Example 7
2-Bromo-5-perfluoro(3,6-dioxadecanoyl)-thiophene
BuLi (3.7 niL, 9.3 mmol) was charged drop wise to a cold (-70 0C) mixture of
THF (40 mL) and 2,5- dibromothiophene (1.0 mL, 8.9 mmol). After 40 min at -70 0C, C4F9OC2F4OCF2CO2Me (4.1 g, 8.9 mmol) and BF3OEt2 (1.3 mL, 10.3 mmol) were added successively turning the clear, colorless mixture light yellow. After stirring overnight, the volatile materials were removed under reduced pressure. The remaining liquid was extracted with 100 mL ether, washed with 2 x 100 mL brine, dried with MgSO4, and stripped to a clear orange liquid. Purification by column chromatography on silica gel afforded a yellow liquid that was dried under vacuum to afford 3.80 g (73%). A larger scale preparation (71 g theoretical yield) afforded 37.8 g (53%) of clean product after it was purified by distillation (bp 55-56 0C, 0.1 mm Torr); a precut of 7.7 g collected from 50-55 0C that was approximately 63% product/37%
C4H3SCORf; a 1.1 g post cut was 91% product and 9% C4HBr2SCORf. IR (neat, KBr plates): 1701 cm-i (s, vco)- 1H NMR: δ 7.52 (d, J- 4.4 Hz, 3-H), 7.91 (dt, J= 4.4 , 1.4 Hz, 4-H). 19F NMR: δ -74.79 (m, CFs), -80.87 (m, COCF2O), -83.07 (m, OCF2CF2O), - 87.61 (m, OCF2CF2O), -88.05 (m, OCF2C3F7), -126.1 (m, CF2CF2CF2CF3).
Example 8
2-Perfluoro(3,6-dioxadecanoyl)-thiophene
BuLi (7.8 niL, 12.5 mmol) was added to a cold (-65 0C) mixture of THF (50 niL) and thiophene (1.0 mL, 12.5 mmol. The clear, colorless solution was warmed to room temperature, cooled to -65 0C, and C4F9OC2F4OCF2CO2Me (5.84 g, 12.7 mmol) and BF3(OEt2) (1.9 mL, 15 mmol) added successively. The yellow solution was stirred cold for 2 hr and then mixed with 2 mL of saturated NH4Cl (aq). The volatile material was removed under reduced pressure, and the residue extracted with 50 mL hexanes.
The solution was filtered, dried with MgSO4, filtered again, and stripped to afford 5.53 g (86%) of clear orange liquid that was clean by NMR spectroscopy. IR: 1700 cm"1 (s, vco). 1H NMR: δ 7.41 (dd, J= 6.0 Hz, 4.0 Hz, 5-H), 8.08 (m, 3-H), 8.33 (dd, J= 4.9 Hz, 1.1 Hz, 4-H). 19F NMR: δ -74.93 (m, CF3), -80.91 (m, COCF2O), -83.12 (m, OCF2CF2O), -87.67 (m, OCF2CF2O), -88.11 (m, OCF2C3F7), -126.18 (m, CF2CF2CF2CF3).
Example 9 5-Perfluoro(3,6,9-trioxadecanoyl)-2,2':5',2"-terthiophene
Under nitrogen, a vessel was loaded with 2,2':5',2"-terthiophene (878 mg, 3.53 mmol) and anhydrous THF (75 mL). The solution was cooled at -78 °C and "BuLi (2.2 mL, 3.5 mmol) was added gradually by syringe. The mixture was stirred cold for 30 min, and then methyl 3,6,9-trioxadecanoate (1.0 mL, 3.8 mmol, 1.1 eq) and BF3OEt2 (0.54 mL, 4.3 mmol, 1.2 eq) were successively added. After another 90 min at -78 °C, sat NH4Cl (aq) (20 mL) was added and the mixture was warmed to ambient temperature and further diluted with ether (100 mL) and water (50 mL). The aq phase was separated, and the yellow-green organic phase was washed with 2 x 100 mL of brine, dried with MgSO4, and filtered.
Analysis by TLC (SiO2 on glass) with 5% EtO Ac/balance hexanes showed the main reaction product with Rf = 0.45. The organic solution was concentrated, adsorbed onto silica gel, and purified by column chromatography (silica gel/hexanes, 1.25 in x 10 in) using hexanes eluent to afford 1.03 g (45%) of bright orange product. 1H NMR: δ
7.15 (dd, J= 5.2 Hz5 3.6 Hz), 7.37 (d, J= 4.0 Hz), 7.44 (dd, J= 3.6 Hz, 1.2 Hz), 7.55 (dd, J= 5.2 Hz, 1.2 Hz), 7.59 (d, J= 4.0 Hz), 7.65 (d, J= 4.0 Hz), 8.02 (dt, 3JHH = 4.0 Hz, 5JHF = 1.6 Hz). 19F NMR: δ -54.9 (t, J= 9.4 Hz, CF3), -74.3 (m, COCF2), -87.4 (m, CF2), - 88.1 (br, 2 CF2- groups), -90.1 (q, J= 9.4 Hz, CF2OCF3).
Example 10
Synthesis of 5,5'"-bis[perfluoro(3,6-dioxadecanoyl)]-2,2':5',2":
5 " ,2 " '-quaterthiophene.
O O
C4F9OCF2CF2OCF2' XF2O(CF2CF2O)C4F9
4 Under a nitrogen atmosphere, a vessel was successively charged with 2-bromo-5- perfluoro(3,6-dioxadecanoyl)thiophene (3.24 g, 5.48 mmol), dry DMF (30 mL), 5,5'- bis(trw?-butylstannyl)-2,2'-bithiophene (2.04 g, 2.74 mmol), and Pd(PPh3)4 (63 mg, 0.055 mmol). The mixture was bubbled through with nitrogen for 20 min, and then stirred at 85 °C overnight. The reaction mixture was transferred into a mixture of EtOAc (100 mL) and CH2Cl2 (100 mL), stirred, and then poured through a 10- 20 μm glass filter frit to isolate the product. The red solid was washed on the frit with methanol (100 mL) and air-dried overnight to afford 2.28 g (70%).
Material used in OTFTs was sublimed at least 2 times. In a typical experiment, 1.01 g was loaded into a train sublimation system. With P = 3 x 10'6 Torr, the source zone was ramped to 240 °C, with the product zone at 180 0C. The product was melted in the source at this point, but not mobile. The source and product zones were ramped to 280 0C and 220 °C, respectively, and the sublimation was done in 30 min. Only a negligible film remained at the source. From the product zone was isolated 884 mg (87% of input). TGA: 1% wt loss at 271 °C; 5% wt loss at 285 °C; no residue at 988°C. DSC (20 °C/min): 185 °C (-71 J/g), reversible melting point. MALDI-TOF mass spectrometry showed a molecular ion isotopic cluster that contained an abundant peak at m/zl 186 1200 (M+), and peaks at M+l (76%), M+2 (55%), M+3 (22%), and M+4 (8%).
Example 11
Synthesis of 5,5""-bis[perfluoro(3,659-trioxadecanoyl)]- 2,2':5',2":5",2'":5'",2'"r- quinquethiophene .
O O
CF3(OCF2CF2)2θCF2 "CF2O(CF2CF2O)2CF3
Under nitrogen, a vessel was charged with Pd(PPh3)4 (65 mg, 0.056 mmol, 0.5 mol% per coupling site), 5-Bromo-5'-perfluoro(3,6,9-trioxadecanoyl)-2,2'-bithiophene (3.54 g, 5.54 mmol), DMF (40 mL), and 5,5'-bis(tri-«-butylstannyl)thiophene (1.83 g, 2.76 mmol). The mixture was bubbled through with nitrogen for 20 min, and then stirred at 90 0C for 20 h. The red mixture was cooled to room temperature and the solid was collected on a 10-20 μm filter frit, washed with 2 x 60 mL isopropanol, and airrdried overnight to afford 2.34 g (71%) of crude, burgundy product.
The material was train sublimed at P = 4 x 10~6 Torr with a source temperature of 315 °C (material is melted) and the product collection zone at 180 °C to afford 2.23 g (67%) of red-purple product. The product was sublimed an additional time before device preparation. 1H NMR (600 MHz, J4-o-dichlorobenzene, 100 0C): Due to the high temperature used during the data collection (the material has very low solubility), broad, singlets were observed for each of the 5 chemically inequivalent protons; δ 7.79, 7.16, 7.10, 7.06, 7.04. 19F NMR (564 MHz, <i4-o-dichlorobenzene, 100 0C): Data was identical to that reported in preparative examples 1 and 4. MALDI-TOF mass spectrometry showed a molecular ion isotopic cluster that contained an abundant peak at m/z 1200 (M+), and peaks at M+l (65%), M+2 (45%), M+3 (20%), and M+4 (10%).
Example 12
Synthesis of 5,5""'-bis[ perfluoro(2,5-dimethyl-3,6- dioxanonanoyl)]-2,2':5\2":5",2'":5"\2"":5"",2 -sexithiophene.
O O
C3F7OCF(CF3)CF2OCF(CF3) " CF(CF3)OCF2CF(CF3)OC3F7
Under a nitrogen atmosphere, a vessel was successively charged with 5~bromo-5'- perfluoro(2,5- dimethyl-3,6-dioxanonanoyl)-2,2'-bithiophene (3.49 g, 4.83 mmol), dry DMF (75 mL), 5,5'-bis(tri-«-butylstannyl)-2,2'-bithiophene (1.80 g, 2.42 mmol), and Pd(PPh3)4 (30 mg, 0.026 mmol). The mixture was bubbled through with nitrogen for 30 min, and then stirred at 100 0C for 5 h. A red ppt formed in the mixture. The solution was cooled to room temperature, and then further with an ice water bath. The solution was poured through a 10-20 μm glass filter frit, and the red solid was washed with methanol (100 mL), hexanes (100 mL), and then air-dried overnight. Yield: 2.79 g, 80%. Material used in OTFTs was sublimed at least 2 times. In one experiment, 994 mg of material was loaded into a train sublimation system and sublimed with P = 2 x 10"6 Torr, source temperature 320 °C, and product zone at 240 °C. The material melted at the source before volatilizing and moving to the product zone. Isolated 918 mg (92% of input).
IR spectroscopy (KBr pellet, vco= 1663 cm-i), combustion analysis, and high resolution mass spectroscopy were consistent with the proposed structure. 1H NMR (400 MHz, tfe-acetone, internal TMS ref to 0 pm): δ 8.18 (m, 1 H), 7.71 (d, J= 4 Hz, 1 H), 7.62 (d, J=4 Hz, 1 H), 7.44 ('d', J= 4 Hz, 2 H), 7.38 (d, J = 4 Hz, 1 H). TGA: 1% wt loss at 365°C; 5% wt loss at 381 °C; no residue at 988 0C. DSC (20 °C/min): 150 0C (-17 J/g), 218°C (-2 J/g), reversible melting point. 19F NMR data was virtually identical to that in preparative examples 3 and 6. A number of the resonances in the 19F data are observed as pairs due to the two asymmetric centers of the fluorinated end group. IR (KBr): 1663 s (vco), 1436 s, 1236 vs, 1202 s, 1151 s, 1079 m, 1029 m, 994 s, 981 m, 790 m cm"1.
High performance liquid chromatography (HPLC) with a THF solution of the product was carried out using an Agilent Model LC/MSD quadrupole mass spectrometer equipped with an atmospheric pressure chemical ionization (APCI) source. The sample solution was injected into a mobile phase of THF/water (1:1) and data were collected over the mass range of 1,000-2,000 Daltons at a scan rate of approximately 2 scans/second. The only significant ions in the spectrum were seen a m/z 1451, m/z 1452, and m/z 1453, corresponding to a compound having a molecular eight of 1,450, consistent with the proposed product.
Example 13
Fabrication and Testing of OTFTs.
OTFTs were fabricated on doped silicon <100> wafers obtained from Silicon Valley Microelectronics (San Jose, CA) with 5 kA aluminum on the backside and 1.5 kA of sputtered AI2O3 on the front. A 0.1 wt % solution of poly(α-methylstyrene) (average Mw ca 100,300 by GPC) was applied to the surface from toluene by spin coating (500 rpm for 20 s, followed by 2000 rpm for 40 s). Samples were placed in a 110 °C oven and baked for 30 min after spin coating. The resultant polymer layer was about 100 A, as measured by single beam ellipsometry. Thin films (~ 600 A) of the perfluoroacyl thiophenes described above were deposited by physical vapor deposition at a pressure ≤ 5 x 10"" Torr. Samples were then moved to another vacuum chamber where gold source-drain contacts (600 A) were evaporated on to the organic film through a polymeric shadow mask.
Figure 2 shows characterization data (/D 1/2 VS VQ curves calculated from ID-VG transfer curves) for thin film transistors made using 5,5'"-bis[perfluoro(3,6- dioxadecanoyl)]-2,2':5',2":5",2'"-quaterthiophene (Example 10) in the semiconductor layer. The data is in the saturated regime, with drain voltages (FD) equal to the maximum gate voltage (VG) in each case. The devices were measured under 10"6 torr vacuum. Data is plotted for both negative-to-positive (-/+) and positive-to-negative (+/-) scans of the gate voltage. The saturation electron mobility (/Ve) was calculated from the slope of the /D 1/2 VS VQ trace at the points indicated using standard metal-oxide-semiconductor field- effect transistor (MOSFET) equations (See Sze, S. M. Physics of Semiconductor Devices; 2nd ed.; John Wiley & Sons: New York, 1981). For the device shown in Figure 2, the mobility was 1.8 cm2/Vs for a negative-to-positive VG scan, and 2.6 cm2/Vs for a positive- to-negative scan. Additional data for other devices on the same wafer are tabulated in Table 1.
Figure 3 shows /D 1/2 VS VQ curves for a thin film transistor made using 5,5""- bis[perfluoro(3,6,9-trioxadecanoyl)]- 2,2':5',2":5",2'":5'",2""-quinquethiophene (Example 11) in the semiconductor layer. Devices were fabricated and tested as described above. Table 2 lists additional data for other devices on the same wafer. With regard to the thin film transistors using the n-channel semiconductor oligothiophene of the invention, the resulting mobility values are the highest values
reported to date for n-channel organic semiconductor materials, and are comparable in performance to p-channel semiconductors such as pentacene.
Table 1.
Additional data for devices made with 5,5r"-bis[perfluoro(3,6-dioxadecanoyl)]-
2,2':5',2":5",2"'-quaterthiophene (Example 10)
Table 2
Additional data for devices made using 5,5""-bis[perfluoro(3,659-trioxadecanoyl)]-
2,2':5',2":5",2"':5'",2""-quinquethiophene (Example 11)
Claims
1. A compound of the formula:
wherein Y is a hydrogen atom, a halogen atom, an alkyl group, and aryl group or a perfluoroether acyl group, p is at least one, and Rf is a perfluoroether group.
2. The compounds of claim 1 of the formula:
wherein each Rf is independently a perfluoroether group, and n is at least 1.
3. The compounds of claim 2 wherein each Rf is a perfluoroalkoxyalkylene group or a perfluoropolyether group.
4. The compounds of claim 2 wherein each Rf corresponds to the formula: Rf'-CKR/VCRf 3)- wherein R f represents a perfluoroalkyl group, Rf 2 represents a perfluorinated polyalkyleneoxy group consisting of perfluoroalkyl eneoxy groups having 1 to 4 perfluorinated carbon atoms or a mixture of such perfluoroalkyleneoxy groups, Rf 3 represents a perfluoroalkyl ene group, x is 0 to 25.
5. The compounds of claim 4 wherein each R/ is independently selected from -CF2- CF2-O-, -CF(CFa)-CF2-O-, -CF2-CF(CF3)-O-, -CF2-CF2-CF2-O-, -CF2-O-, -CF(CF3)-O-, and -CF2-CF2-CF2-CF2-O-.
6. The compounds of claim 4 wherein each Rf 3 is independently selected from -CF2- CF2-, -CF(CF3)-CF2-, -CF2-CF(CF3)-, -CF2-CF2-CF2-, -CF2-O-, -CF(CF3)-, and -CF2-CF2- CF2-CF2-.
7. The compounds of claim 4 wherein x is 1 to 4.
8. The compounds of claim 2 wherein each Rf is Rf 1-O-[CF(CF3)-CF2O]X-CF(CF3)- wherein Rf 1 is a perfluoroalkyl group and x is at least one.
9. The compounds of claim 4 wherein Rf 1 represents a perfluorinated alkyl group having 1 to 6 carbon atoms.
10. The compounds of claim 2 wherein n is 3 to 6.
11. The compounds of claim 2 wherein Rf is
F(CFCF2O)i_4CF- CF3 CF3
12. A method of preparing a compound of claim 2 comprising a. reacting a bis-trialkylstannyl (oligo)thiophene with a b. 2-halo-5-perfluoroetheracyl thiophene or a 5-halo-5'-perfluoroetheracyl oligothiophene c. in the presence of a palladium catalyst.
13. The method of claim 12 comprising the steps of reacting a bis-trialkylstannyl thiophene of the formula
wherein each R is selected from a lower alkyl group, with a 2-halo-5-perfluoroetheracylthiophene of the formula: where m is 1 to 3, and Rf is a perfhioroether group, c) in the presence of a palladium catalyst.
14. The method of claim 13 wherein the compound of the formula
is prepared by brominating a compound of the formula:
each m is 2 to 3, and Rf is a perfluoroether group.
15. The method of claim 14 where the compound of the formula
is prepared by treating of the oligothiophene compound of the formula:
with an alkyl lithium compound, followed by quenching the thienyl anion with a perfluorinated ether ester of the formula Rf-CO-OR, where Rf is a perfluorinated ether group and R is an alkyl group, in the presence of a Lewis acid catalyst, where m is 1 to 3.
16. The method of claim 15, where the Lewis acid catalyst is a boron trifluoride etherate.
17. The method of claim 14 where the compound of the formula
is prepared by treating of the 2,5-dihalothiophene with an alkyl lithium compound, followed by quenching the thienyl anion with a perfluorinated ether ester of the formula Rf-CO-OR, where Rf is a perfluorinated ether group and R is an alkyl group, in the presence of a Lewis acid catalyst, where m is 1 to 3.
18. A n-channel semiconductor device wherein the semiconductor layer comprises a compound of the formula comprising any of claims 1-11.
19. The semiconductor device of claim 18, further comprising a conducting layer, a dielectric layer, or a combination thereof adjacent to the semiconductor layer.
20. The semiconductor device of claim 18, wherein said semiconductor device comprises an organic thin film transistor.
21. The semiconductor device of claim 18, further comprising a source electrode and a drain electrode in contact with the semiconductor layer, wherein the source electrode and the drain electrode are separated by an area on the surface of the semiconductor layer.
22. The semiconductor device of claim 18, further comprising a conducting layer adjacent to one surface of the semiconducting layer and a dielectric layer adjacent to an opposite surface of the semiconducting layer.
23. A method of preparing an organic thin film transistor, said method comprising: providing a gate electrode; depositing a gate dielectric layer on a surface of the gate electrode; preparing a semiconductor layer adjacent to the gate dielectric layer opposite the gate electrode, said semiconductor layer comprising a compound of the formula of any of claims 1-11.
24. The method of claim 23 further comprising the step of positioning a source electrode and a drain electrode on a surface of the semiconductor layer that is opposite the gate dielectric layer, wherein the source electrode and the drain electrode are separated from each other in an area on the surface of the semiconductor layer.
25. The method of claim 23, further comprising depositing a surface treatment layer between the gate dielectric layer and the semiconductor layer.
26. A method of preparing an organic thin film transistor, said method comprising: providing a gate electrode; depositing a gate dielectric layer on a surface of the gate electrode; positioning a source electrode and a drain electrode adjacent to the gate dielectric layer opposite the gate electrode, wherein the source electrode and the drain electrode are separated by an area over the gate dielectric layer; preparing a semiconductor layer on a surface of the source electrode, on the surface of the drain electrode, and in the area between the source electrode and the drain electrode, said semiconductor layer comprising a compound of any of claims 1-11.
27. A Schottky diode comprising the device of claim 18, wherein a first metal is in contact with a first surface of said semiconductor, and a second metal in contact with a second surface of said semiconductor layer.
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