JP3249971B2 - エレクトロルミネセント素子 - Google Patents
エレクトロルミネセント素子Info
- Publication number
- JP3249971B2 JP3249971B2 JP50602890A JP50602890A JP3249971B2 JP 3249971 B2 JP3249971 B2 JP 3249971B2 JP 50602890 A JP50602890 A JP 50602890A JP 50602890 A JP50602890 A JP 50602890A JP 3249971 B2 JP3249971 B2 JP 3249971B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- polymer
- contact layer
- contact
- electroluminescent device
- 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.)
- Expired - Lifetime
Links
- 239000004065 semiconductor Substances 0.000 claims abstract description 65
- 229920000642 polymer Polymers 0.000 claims abstract description 58
- 229920000547 conjugated polymer Polymers 0.000 claims abstract description 52
- 229920006254 polymer film Polymers 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 239000002800 charge carrier Substances 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000000151 deposition Methods 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 230000005684 electric field Effects 0.000 claims abstract description 10
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000001424 substituent group Chemical group 0.000 claims abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims abstract description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 3
- 239000010410 layer Substances 0.000 claims description 201
- 238000002347 injection Methods 0.000 claims description 34
- 239000007924 injection Substances 0.000 claims description 34
- 229920000553 poly(phenylenevinylene) Polymers 0.000 claims description 31
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 229910003437 indium oxide Inorganic materials 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000010931 gold Substances 0.000 claims description 10
- -1 Phenylene vinylene Chemical group 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 238000007740 vapor deposition Methods 0.000 claims description 4
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 229910001922 gold oxide Inorganic materials 0.000 claims 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims 1
- 239000002195 soluble material Substances 0.000 claims 1
- 239000002344 surface layer Substances 0.000 claims 1
- 230000005855 radiation Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 28
- 239000000463 material Substances 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000005401 electroluminescence Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000010409 thin film Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000265 Polyparaphenylene Polymers 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000001429 visible spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000001659 ion-beam spectroscopy Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 2
- RAOIDOHSFRTOEL-UHFFFAOYSA-O thiolan-1-ium Chemical compound C1CC[SH+]C1 RAOIDOHSFRTOEL-UHFFFAOYSA-O 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910000878 H alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000042032 Petrocephalus catostoma Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- TWXDDNPPQUTEOV-FVGYRXGTSA-N methamphetamine hydrochloride Chemical compound Cl.CN[C@@H](C)CC1=CC=CC=C1 TWXDDNPPQUTEOV-FVGYRXGTSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000001552 radio frequency sputter deposition Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- 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
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/114—Poly-phenylenevinylene; Derivatives thereof
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electroluminescent Light Sources (AREA)
- Illuminated Signs And Luminous Advertising (AREA)
- Luminescent Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Led Devices (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
- Control Of El Displays (AREA)
- Control Of Indicators Other Than Cathode Ray Tubes (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Description
し、一層詳細には、発光層が半導体であるエレクトロル
ミネセンス(EL)素子およびその製造方法に関する。
により発光するよう構成されている。このように使用さ
れる半導体における物理的過程に対する一般的な作用
は、半導体の相対する電極から半導体に注入される電子
−正孔対の放射結合を通して行われる。その一例を挙げ
ると、ガリウムとリン、および同様なIII族−V族の半
導体を基礎とする発光ダイオードがある。
ものの、その大きさが非常に微小であるために大きな領
域を有する画面に使用するに際しては、困難を伴うばか
りか不経済でもある。
料は幾種類か知られており、無機半導体の中、ZnSに最
も多大な努力が向けられた。この系は無視できない実用
上の欠点、第1に信頼性が乏しいという問題が存在す
る。前記ZnSに係るメカニズムの一例は、強電界下にお
いて、半導体を通って一種のキャリヤが加速されること
により、放射発光によって緩和する半導体の局部的励起
が生じることであると考えられる 有機材料の中、アントラセン(anthracenc)、ペリレ
ン(perylene)、そしてコロネン(coronene)のような
単体芳香族分子(simple aromatic molecules)がエ
レクトロルミネセンスを示すことが知られている。
にそれらが信頼性を欠くばかりか、これらの有機層と電
流注入電極層(current−injecting electrode layer
s)との接合が困難なことである。
く、再結晶傾向が強いという欠点がある。
着などの技術は、膜の品質の劣化、能動物質の希釈、さ
らには、製造コストの高騰を招く。
ミネセンス素子は、米国特許3,621,321号に開示されて
いる。この素子は、多量の電力を消費し、且つ低ルミネ
センスであるという不都合を有している。
265号には、発光層を2層からなる構造としたエレクト
ロルミネセンス(EL)素子が記載されている。
述の不都合を有する有機材料である。
は少なくとも前記不都合を低減化することを可能とする
エレクトロルミネセンス(EL)素子およびその製造方法
を提供することを目的とする。
密度で薄層からなるポリマー膜形状の半導体層を含むエ
レクトロルミネセンス素子を提供するものであり、第1
接触層(first contact layer)は、半導体層の第1
の表面と接し、第2接触層(second contact layer)
は、半導体層の第2の表面と接する。半導体層のポリマ
ー膜は第2接触層を第1接触層に対して正にするように
半導体層を介して第1および第2の接触層に電界をかけ
ると電荷キャリヤ(charge carriers)が半導体層に注
入され、半導体層から発光がなされるように十分に低い
濃度の外部電荷キャリヤを有していることを特徴とする
エレクトロルミネセンス素子が提供される。
から電荷キャリヤ(charge carriers)がエレクトロル
ミネセンス素子に注入されることより発光することを応
用した共役ポリマーからなる半導体に発見の基礎をおい
ている。
らは、光学変調器(optical modulator)に用いられる
ことが欧州特許出願第0294061号で検討されている。こ
の場合には、第1の電極と第2の電極の間に位置する変
調構造の能動層(active layer)にポリアセチレンが
用いられている。光学変調効果を発生させる能動層(ac
tive layer)に空気電荷領域を形成するために、一つ
の電極と能動層(active layer)との間に絶縁層(ins
lating layer)を設けることがある。そのような構造
では、電子の空孔(charge space)が存在するために
その崩壊が発光に寄与する電子−正孔対(elector−hol
e pairs)の構成を妨げるため、エレクトロルミネセン
ス素子には不向きである。いずれにせよ、欧州特許出願
第0294061号のエレクトロルミネセンス素子では、光学
変調効果がそれによって破壊されるので、全く望ましく
ない。
ed Polymer)はポリ(p−フエニレンビニレン)であ
るのが好ましく、第1の電荷注入接触層(first charg
e injection contact layer)は、一側の表面に薄い
酸化物層が形成されたアルミニウムの薄層からなり、半
導体層の第1の表面は前記酸化物層と接し、第2の電荷
注入接触層(second charge injection contact la
yer)はアルミニウムまたは金の薄層である。
触層(first contact layer)がアルミニウム、若し
くはマグネシウムと銀の合金で、第2接触層(second
contact layer)は、酸化インジウムである。
り、接触層の一つは非晶質シリコンからなり、他方の接
触層は、アルミニウム、金、マグネシウム−銀合金、酸
化インジウムからなる群のうちから選択される。
うちのいずれかを基板に積層し、PPVの薄層を付与し、
そして、その上に前記積層されなかった接触層を積層す
ることによって達成される。
ら5マイクロメータ(μm)の範囲の均一な厚さを有
し、共役ポリマーは1エレクトロンボルト(eV)から3.
5エレクトロンボルト(eV)の範囲で半導体バンドギャ
ップを有する。その上、ポリマー膜の電界発光領域にお
ける共役ポリマーの割合は、膜内に存在する共役ポリマ
ー中での電荷移動の浸透閾値を達成するのに十分であ
る。
ポリマーから成る薄い緻密な重合体膜の形状の半導体層
を、前駆体ポリマーの薄膜をポリマー薄膜として基板上
に付着させ、次に付着した前駆体ポリマーを高温に加熱
して共役ポリマーを生成する工程によって基板上に付着
させ、第1の接触層の薄膜を前記半導体層の第1の表面
と接して設け、そして、第2の接触層の薄膜を前記半導
体層の第2の表面と接して設けるエレクトロルミネセン
ス素子を製造する方法であって、ポリマー膜が、第2の
接触層を第1の接触層に対して正にするように前記半導
体層と接した第1及び第2の接触層間に電界をかける
と、電荷キャリヤが半導体層に注入されて、半導体層か
ら発光がなされるように十分に低い濃度の外部電荷キャ
リヤを有していることを特徴とするエレクトロルミネセ
ンス素子の製造方法が提供される。
π電子系を有するポリマーを意味する。非極在化したπ
電子系は半導体特性をポリマーへ付与し、そして、ポリ
マーの骨格に沿って高い移動度を有する正と負の電荷キ
ャリヤを担持する能力をポリマーに付与する。
り、Journal of Molecular Electronies4(1988)Ja
nuary−March,No.1,の37ページから46ページで検討され
ている。
る。すなわち、正の接触層は、ポリマー膜に正の電荷キ
ャリヤを注入し、負の接触層は、ポリマー膜に負の電荷
キャリヤを注入する。前記電荷キャリヤは、結合して放
射的に崩壊する電荷対を形成する。これを達成するため
に、正の接触層は高い仕事関数を有するように、また、
負の接触層は低い仕事関数を有するように選択するのが
好ましい。従って、負の接触層は、電子注入材料、例え
ば、ポリマー半導体層と接触し、金属あるいはドープ半
導体(a doped semiconductor)のような電子注入材
(electric−injecting material)から構成され、回
路を介して外部電位を印加することによって負電位を生
じる時、電子のポリマー半導体層への注入がなされる。
正の接触層は、例えば、金属やドープ半導体(a dope
d semiconductor)のような正孔注入材料(hole−inje
cting material)から構成され、ポリマー半導体層と
接触し、外部電位を印加することによってポリマー半導
体に対し正にされた時に、ポリマー半導体層に一般に正
孔と呼ばれる正の電荷が注入される。
ためには、ポリマー膜は非発光性再結合の中心として作
用する欠陥が実質的に存在しないことを必要とする。そ
のような欠陥はエレクトロルミネセンスを妨げるからで
ある。
除されたポリマー膜を意味する。
injecting material)に加えて、電子対正孔のEL層へ
の注入比を制御し、且つ放射崩壊が接触層の電子注入材
(electric−injecting material)から離れて生じる
ことを確実にするのに役立つ材料、好ましくは有機材料
を含むことが可能である。
ymer)は、好適には、一種類の共役ポリマーあるいは、
共役ポリマーを含む単一コポリマーから構成される。ま
たあるいは、共役ポリマー(conjugated polymer)か
らなる膜は、共役ポリマー、またはコポリマーと別の適
当なポリマーとの混合物から構成されることも可能であ
る。
である。
上昇および圧力圧迫を原因とする亀裂の発生に対する阻
止能力並びに縮み、膨張、再結晶あるいは他の形質変化
に対する抵抗性を有するべきである。
り、イオン/原子移動工程に対して回復性があるべきで
ある。
がら記述する。
−フエニレンビニレン)[PPV]であり、下記構造式に
おいて、フェニレンリングは、必要に応じて各々独立し
てアルキル基(好適にはメチル基)、アルコキシ基(好
適にはメトキシ基若しくはエトキシ基)、ハロゲン(好
適には塩素若しくは臭素)またはニトロのなかから選択
され置換される。
他の共役ポリマーもまた、本発明に係るエレクトロルミ
ネセンス(EL)素子のポリマー膜として使用されるのに
適している。
える、例えば、フェニレンリングをアントラセンあるい
はナフタレン環系を置換することによって得られる、以
下のような構造を有するポリマー。
して説明した種類の一あるいはそれ以上の数の置換基を
有することができる。
換することによって得られる、以下のような構造を示す
ポリマー。
して先に述べた種類の一あるいはそれ以上の数の置換基
を有してもよい。
いはiiにおいて説明した他の環系の一つ)に結合したビ
ニレン部分の数を増やすことによって得られる以下のよ
うな構造を示すポリマー。
示す。
よい。
ネルギーギャップを有する。このことは全可視スペクト
ル部に渡って異なる波長で発行するエレクトロルミネセ
ンス素子を構成することを可能とする。
「前駆体」ポリマーを化学処理および/または熱処理す
ることによって製造することができる。後者の前駆体ポ
リマーは引き続いて脱離反応によって共役ポリマーに添
加する前に精製または所望の形状に前処理することがで
きる。
駆体を使用することにより同様の方法で導電性基板に付
着することができる。
に対する溶解度が高いポリマー前駆体を用いるのが有利
な場合がある。アルコキシ基(通常メトキシ)あるい
は、ピリジニウム基のような親水性の低い基によって前
駆体中のスルホニウム部を置き換えることにより有機溶
媒に対する溶解度を高めることが達成できる。
1図に示されるような反応図式に用いた方法により、導
電性基板上に付着される。スルホニウム塩単量体(II)
は、水溶性、水エタノール混液、若しくはメタノール中
で前駆体ポリマー(III)に合成される。そのような前
駆体ポリマー(III)の溶液は、ホトレジスト処理のた
めに半導体産業で用いられている一般的なスピンーコー
ティング技術により導電性基板上に付着することができ
る。次に、得られた前駆体ポリマー(III)膜は、通例2
00℃から350℃の温度に加熱処理してポリ(フエニレン
ビニレン)(I)に転化される。
合、そしてPPVへのための熱転化のために必要な詳細な
条件は、文献、例えば、D.D.C.BradleyによるJ.Phys.D
(applied Physics)、20、1389(1987)およびJ.D.St
enger Smith、R.W.LenzとG.WegnerによるPolymer、3
0、1048(1989)に記載されている。
厚さで得られることを見出した。これらのPPV膜は、ご
くわずなピンホールしかみられない。PPV膜は、約2.5eV
(500nm)の半導体エネルギーギャップを有する。
テトラヒドロチオフェニウム成分に置き換えることがで
きる。直鎖ジアルキルスルホニウムは、テトラヒドロチ
オフェニウムに置換可能である。
は、ポリ(フェニレン)である。
1、3−ジエンの生化学的に合成される誘導体を出発物
質として製造することができる。これらの誘導体は、ラ
ジカル開始材を使用することによって重合して単一溶媒
に溶ける前駆体ポリマーとすることができる。このポリ
(フェニレン)の製造は、Ballard et al、J.Chem.Co
mm.954(1983)により詳細に記載されている。
スピンコートされ、そしてその後通例140℃から240℃の
範囲で熱処理されて共役ポリ(フェニレン)ポリマーに
転換される。
ェニレンコポリマーを得るように行うことができる。
できる材料は、主共役鎖に結合した巨大な側鎖基の存在
によって、あるいは、少なくとも一つ以上の成分が非共
役である共重合の構造体に共役ポリマーを含むことによ
り、溶液による加工あるいは溶解による加工のいずれか
による共役ポリマーである。例えば、前者の例には以下
のようなものが含まれる。
ン)[PDPV]は、両方のビニレンの炭素がフェニレンリ
ングにより置換されているアリーレンビニレンポリマー
である。それは、薄い膜を形成できるように普通の有機
溶媒に解ける。
レン)とポリ(1、4−フェニレンジフェニレンビニレ
ン)ポリマーはPPVの類似物質であり、それぞれ一つあ
るいは両方のビニレンの炭素がフェニル基と置換されて
いる。それらは各々有機溶媒に溶け、キャストまたはス
ピン被覆されて薄膜となる。
キルは、プロピル、ブチル、ペンチル、ヘキシル、ヘプ
チル、オクチル、デシル、ウンデシル、ドデシル等のい
ずれか一つ)は普通の有機溶媒中で溶液加工可能であ
り、また、長いアルキル序列(アルキルはオクチルと等
しいかそれ以上に長い)は溶融加工可能である。
(3−アルキルチオフェン)ポリマーと類似であること
が予想される。
5−ジアルコキシ−p−フェニレッビニレン)ポリマー
は溶解加工可能である。
がフェニル基に置換されたポリアセチレンの誘導体であ
る。この置換によっては、材料は可溶性にされる。
電性基板上に必要とされるポリマーからなる薄い均一な
膜が容易に得られるように、他のポリマーと共役ポリマ
ーが混合された混合ポリマーが適している場合もある。
マーまたはポリマーブレンドを用いる時、前記共役ポリ
マーの膜を組み入れるエレクトロルミネセンス素子の活
性部位は、コポリマーあるいはポリマーブレンドのパー
コレイションしきい値と同じかそれ以上に大きい多量の
共役ポリマー部位を含まなければならない。
ギャップおよび/または多くの電荷種を含むポリマー層
を有する複合層として形成されているので、例えば、電
荷注入層からエレクトロルミネセンス素子の領域内の注
入電荷の集中が達成される。複合層は、ポリマー層の連
結析出によって形成することができる。種々の膜がスピ
ン若しくはドローコーティングにより共役ポリマーに前
駆体の形で付着される場合、共役ポリマーへの転化工程
によって膜が溶解しないようにされるので、その後の層
をこの先に付着された膜を溶解することなく同様に付与
することができる。
施することができるかを示すために添付図面とともに実
施例を示す。
示す図であり、 第2図並びに第3図は、本発明に係るエレクトロルミ
ネセンス素子の概略図であり、 第4図は、第2図並びに第3図に記載されたエレクト
ロルミネセンス素子の発光出力を示すグラフ、 第5図並びに第6図は、本発明に係る他の実施例に係
るエレクトロルミネセンス素子の夫々電流対発光、およ
び出力強度対印加電圧を示すグラフであり、そして 第7図並びに第8図は本発明のさらに他の実施例に係
る電流出力と電界発光強度を示すグラフである。
センス(EL)素子の構造を以下に説明する。
酸塩ガラス1の上面に第1の電荷注入接触層2を形成し
た。電荷注入接触層は、約20nmの厚さの層を作るための
シャドウマスクを介してアルミニウムを熱蒸着させて形
成した。前記シャドウマスクを使用して幅2mm、間隙2mm
および長さ15mmの一連の平行に並ぶ細片状であるパター
ンを形成する。得られたアルミニウム電荷注入接触層を
次に薄い表面酸化物層3を形成するために空気にさらし
た。このようにして電子注入接触層を形成した。
体メタノールを前記の結合基板にスピンコーティングし
た。これは、結合基板の全表面にポリマー溶液を塗布
し、次にその上面を水平に保持して5000r.p.m.までの速
度で軸の回りに回転することによって達成された。次
に、得られた基板とポリマー前駆体層をバキュームオー
ブンで300℃の温度で加熱した。この加熱処理によっ
て、前駆体ポリマーはPPVに変換された。得られたPPV膜
4は100から300nmの厚さであった。必要最低限の膜の厚
さを膜のコンダクタンスによって設定し、下限は20nm程
度である。しかしながら、好ましい厚さの範囲は20nmか
ら1μmの範囲である。
るいはアルミニウムを蒸着させて形成される。シャドウ
マスクを再度使用してPPV膜の表面上にパターンを形成
し、幅2mm、間隙2mm、長さが15mmの平行に並ぶ一連の細
長い小片を第1の電荷注入接触層に直角に回転して形成
した。第2の電荷注入接触層の厚さは、20から30nmの範
囲であった。このようにして正孔注入接触層を形成し
た。
に垂直にエレクトロルミネセンス(EL)素子から発光を
なすために透明、若しくは半透明であることが望まし
い。本実施例では、このことは金、若しくはアルミニウ
ムの層が30mm以下の厚さである時になされる。PPV層の
厚さが約200nmの素子に関し、電荷注入および強力なエ
レクトロルミネセンスの発現に対するしきい電圧は、約
40ボルトである。この電圧は、2×106Vcm-1のしきい電
界を印加する。素子の出力は、100KHzまでの周波数には
ほとんど依存しなかった。このことはエレクトロルミネ
センス(EL)素子の応答時間が非常に短く、そして10マ
イクロセカンドより速いことを示している。エレクトロ
ルミネセンス(EL)素子を使用する時、特別な用心をす
ることなく空気中で作用し、機能低下の兆候はなにも示
さなかった。
分光され、シリコン光起電力のセルで検出し、計温は、
室温20℃で、且つ、低温下において、光学通路を有する
低温保持装置に素子を保持して行った。その結果を第4
図に示す。エレクトロルミネセンス(EL)素子のスペク
トルは、ピークが温度によってその位置をわずかにシフ
トして0.15eVだけ異なって690nmから500nm(1.8eVから
2.4eV)のスペクトル範囲で発光することを示してい
る。
事関数を有するので電子注入接触層は、(非晶質あるい
は結晶性)のn−ドープシリコン、酸化膜を有するシリ
コン、純粋、若しくは金などの他の金属との合金である
アルカリ、およびアルカリ土類金属類である。また、
“n形ドープ”共役ポリマーの薄層を、金属層と電界発
光ポリマー層との間に介在させて電子注入接触層を形成
することもできる。
関数を有するので正孔注入層として用いられるのに適し
た他の材料は、インジウム/スズ酸化物(可視スペクト
ル部で透明である)、白金、ニッケル、パラジウム、お
よび黒鉛である。また、電気化学的に重合されたポリピ
ロール、ポリチオフェン等の“p形ドープ”共役ポリマ
ーの薄膜を金属層と電界発光ポリマー層との間に入れる
ことによって正孔注入層を形成することもできる。
なわち、白金のような融点温度が特に高い金属を除いた
全ての金属は、蒸着により付着することができる。イン
ジウム/錫の酸化物を含む全ての合金は、DCあるいはRF
スパッタリング法および電子ビーム蒸着法を用いて付着
させることができる。非晶質シリコンの付着はシリコン
とホスフィンなどのドーピング材との混合物からグロー
放電付着法によって行うことができる。
て付着される。まず、導電性であるが透明な酸化インジ
ウムを酸素の存在下にインジウムターゲットからイオン
−ビームスパッタリングする方法によって基板上に付着
させた。
0.1nm/秒の付着速度でのインジウムターゲットからのイ
オン−ビームスパッタリングによって、代表的に5x10-4
Ωcmの抵抗率を有する透明な酸化インジウムの膜が形成
された。代表的に、100nmの厚さによって単位面積当り
約50Ωの比シート抵抗が与えられる。そのような膜は可
視スペクトル部において90%より好ましい光学透過係数
を有している。
酸化インジウム層上に付着させる。最後に、アルミニウ
ムの上部接触層を代表的には50nmの厚さに蒸着によって
付着させる。この構造体を操作すると、酸化インジウム
接触層が正の接触層として、及びアルミニウム接触層が
負の接触層として機能する。発光は酸化インジウム層を
通して見られる。
する構造体の結果を第5図及び第6図に示す。発光に関
連する電流のしきい値は第5図において約14Vであるこ
とがわかる。素子の分光的に総和した光出力の強度の変
動を第6図に電流の関数として示す。
2と同じである。本実施例では、蒸着によって銀とマグ
ネシウムとの合金を付着させて、負の接触層として作用
する上部接触層を形成する。蒸着は1:10のモル比の銀及
びマグネシウム粉体の混合物をポート中で加熱すること
によって実施され、代表的に50nmの厚さの膜が付着され
た。
として用いるのが望ましい。銀を加えて合金とするの
は、ポリマー層に対する金属膜の接触性を良くし、酸化
に対する耐性が改善される。この例における電流/電圧
特性およびエレクトロルミネセンス特性は、実施例2に
記載のものと類似していた。
リコン−水素合金層及び正の電極として作用する酸化イ
ンジウムを用いて製造した。アルミニウムまたはクロム
の蒸着金属接触層を有するガラス基板を使用する。次
に、非晶質シリコン−水素膜を以下に詳細に説明する高
周波加熱(RF)スパッタリングによって付着させた。
び液体窒素冷却ゲッターを有し、8cmのターゲット−基
板間隔で操作される。処理室は5x10-8mbarのペース圧力
である。マグネトロンターゲットに3mmの厚さにn−ド
ープSiウェハ層を担持させる。試料を付着させる前に1
〜2時間予備スパッタリングすることによってこれらの
ターゲットを浄化する。上記のようにして製造された基
板を、3cmの厚さのCu及びAl基板の温度が250〜300℃に
なるように放射加熱する。基板を約6r.p.m.で回転す
る。使用するスパッタリングガスは0.007〜0.013mbarの
圧力において30%のH2を含むArであり、蒸着の間連続し
て処理室に通す。使用するRF出力は2Wの反射出力を有し
て250Wである。付着速度は代表的には12nm/分であり、
この場合1μmの膜圧に対し1.5時間の付着時間を要す
る。
08Ωcmの直流抵抗率を有している。この抵抗率は試料の
上側または下側に長さ3mm、間隔0.25mmで二つのAlパッ
ドを蒸着し、それら二つのコンタクト間の抵抗を測定す
ることによって求めた。
載したように、PPVの層を付与し、引き続き実施例2で
記載した手順を用いてこのPPV層の上に直接酸化インジ
ウム層を付着させた。
素層の厚さ1μm、PPV層の厚さ40nm及び酸化インジウ
ム層の厚さ250nmの構造体に関して得られた結果を第7
図及び第8図に示す。第7図に、順バイアス(酸化イン
ジウム層が正)における素子の電流体電圧特性を、また
第8図に電流に対する総和光出力の変動を示す。電荷注
入及び発光は約17Vで開始され、本実施例の場合抵抗性
のシリコン−水素層が存在するために、このしきい値を
越えた電流の上昇は、例えば、第5図に示すように、そ
のような層を有しない構造に見られるよりなだらかであ
る。
接触層に対して酸化インジウム接触層が負)においてよ
り弱い電界発光を示した。しかしながら、順バイアスで
操作するのが好ましい。
Alと置き換えたことを除いて、実施例4におけるように
製造した。最上層を、厚さ約20nmの厚さとしてなる構造
物は電子発光を示す層である。これらの素子は、上述し
た各実施例と同様の特性を示す。
した接触層にも適用することができる。
ためのそれ自体公知の他の方法がある。シリコンの場
合、これは、シランのグロー放電と蒸着を含む。付着方
法は、蒸着、RFおよび直流スパッタリングを含む。
と、接触層における所望の光学的透明度によって決定さ
れる。電荷注入の容易性は、電荷注入接触層を複合層と
して構成することで改善される。この複合層は、正孔お
よび電子を夫々注入するための酸化および還元共役ポリ
マーの薄膜層を含有する。これらの特別な共役ポリマー
層は、活性状態の電界発光ポリマーと同様であってもよ
い。このような物質をドープする方法は、この分野にお
いては良く知られており、「導電性ポリマーハンドブッ
ク」(ティ.ジェイ.スコッテイム(T.J.Skotheim))
に良く書かれている。
直に発光させるため透明または半透明であるのが好まし
いが、例えば、素子の平面内での放射が要求されない場
合には必ずしもその限りではない。
界は、スピンコーティングに使用することができる基板
のサイズによって決定される。例えば、このようにし
て、直径15cmのシリコンウエファのコーティングが行わ
れる。さらに、広い面積のコーティングを行うために
は、ドローコーティングなどの技術がその代わりに用い
られる。従って、平方メートルの範囲の面積を有する共
役ポリマーを用いたエレクトロルミネセンス素子を構成
することが実現できる。
種々の用途に適用することができる。それは、従来、半
導体LEDが使用されていたところに使用することができ
る。それはまた従来液晶が使用されていたところにも使
用することができる。
大面積液晶ディスプレイが遭遇した基板の平面性及び間
隔に関する問題を、大面積エレクトロルミネセンス素子
は解決することができる。エレクトロルミネセンス素子
はマトリックス−アドレス型ディスプレイ、例えばテレ
ビジョン及びコンピュータディスプレイに特に適してい
る。マトリックス−アドレス型ディスプレイに使用する
エレクトロルミネセンス素子の一例を第3図に示す。こ
こでは、各電荷注入接触層が半導体層のいずれかの面に
細長くいく筋にも付着され、一方の接触層の細片が他方
の接着層の細片と直交している。ディスプレイの画素と
呼ばれる個々のエレクトロルミネセンス素子、すなわち
半導体層の各領域のマトリックスのアドレス指定は低い
電荷注入接触層及び高い電荷注入層を選択することによ
って達成される。さらに、エレクトロルミネセンス素子
は上記のように応答速度が速いので、テレビジョン受像
機として使用するのに適しており、特に発光色を共役ポ
リマー、またその半導体バンドギャップを選択すること
によって制御することができるので、混色に適するグリ
ーン、レッド及びブルー画素を用いるカラーディスプレ
イがエレクトロルミネセンス素子中に異なる共役ポリマ
ーを配置することによって可能となる。
び/または薄膜導波管と効果的に光学結合させて光源と
して作用するように光通信への用途が考えられる。同様
な用途が“サイエンス・アンド・テクノロジー・イン・
ジャパン”、8〜14頁(1989年7月)に「オプチカル・
インフォメーション・プロセッシング」という題名でサ
トシ・イシハラによって記載されている。
Claims (25)
- 【請求項1】少なくとも一つの共役ポリマーからなる緻
密なポリマー膜の形状を呈し発光色を制御する半導体バ
ンドギャップを有する半導体層と、素子に電界をかける
ことによって第1のタイプの電荷キャリヤが前記半導体
層に放出されるように選択された第1の接触層と、前記
素子に電界をかけることによって第2のタイプの電荷キ
ャリヤが前記半導体層に放出されるように選択された第
2の接触層とからなり、前記半導体層のポリマー膜は、
半導体層を横断して前記第1と第2の接触層の間に電界
をかけたときに前記第1の接触層に対して第2の接触層
を正にすべく前記第1と第2の電荷キャリヤが前記半導
体層の中に注入されて共役ポリマー電荷キャリヤ対を形
成するように結合されて放射して崩壊することにより、
前記共役ポリマーから発光が行われるほどに十分に低い
濃度の外部電荷キャリヤを有することを特徴とするエレ
クトロルミネセンス素子。 - 【請求項2】請求項1記載のエレクトロルミネセンス素
子において、共役ポリマーが式 【式1】 [式中、フェニレン環は、必要に応じてアルキル(好適
にはメチル)、アルコキシ(好適にはメトキシまたはエ
トキシ)、ハロゲン(好適には塩素または臭素)または
ニトロの中からそれぞれ独立して選択される一つあるい
はそれ以上の置換基を有していてもよい]のポリ(p−
フェニレンビニレン)[PPV]であることを特徴とする
エレクトロルミネセンス素子。 - 【請求項3】請求項1または2記載のエレクトロルミネ
センス素子において、前記ポリマー膜は10nmから5μm
の実質的に均一な厚さを有することを特徴とするエレク
トロルミネセンス素子。 - 【請求項4】請求項1乃至3のいずれかに記載のエレク
トロルミネセンス素子において、共役ポリマーが1eVか
ら3.5eVの範囲内で半導体のバンドギャップを有するこ
とを特徴とするエレクトロルミネセンス素子。 - 【請求項5】請求項1乃至4のいずれかに記載のエレク
トロルミネセンス素子において、ポリマー膜のエレクト
ロルミネセンス領域において、共役ポリマーの割合はフ
イルムに存在する共役ポリマーにあってキャリヤを移動
させるために十分な浸透しきい値を有するものであるこ
とを特徴とするエレクトロルミネセンス素子。 - 【請求項6】請求項1乃至5のいずれかに記載のエレク
トロルミネセンス素子において、第1の電荷キャリヤの
注入接触層は薄い酸化層を形成したアルミニウムからな
る一つの薄い表面層を有し、半導体層の第1の表面が前
記酸化層と接触していることを特徴とするエレクトロル
ミネセンス素子。 - 【請求項7】請求項1乃至6のいずれかに記載のエレク
トロルミネセンス素子において、第1の接触層はアルミ
ニウム、若しくはマグネシウムと銀の合金からなるグル
ープから選択されることを特徴とするエレクトロルミネ
センス素子。 - 【請求項8】請求項6記載のエレクトロルミネセンス素
子において、第2の電荷キャリヤ注入接触層はアルミニ
ウムと金からなるグループから選択されることを特徴と
するエレクトロルミネセンス素子。 - 【請求項9】請求項1乃至8のいずれかに記載のエレク
トロルミネセンス素子において、第1と第2の電荷キャ
リヤ注入接触層は少なくとも一つが半透明体であること
を特徴とするエレクトロルミネセンス素子。 - 【請求項10】請求項7記載のエレクトロルミネセンス
素子において、第2の接触層は酸化インジウム若しくは
酸化インジウムスズであることを特徴とするエレクトロ
ルミネセンス素子。 - 【請求項11】請求項1乃至5のいずれかに記載のエレ
クトロルミネセンス素子において、第1の接触層は非晶
質シリコンからなり、第2の接触層はアルミニウム、金
および酸化インジウムから構成されるグループから選択
されることを特徴とするエレクトロルミネセンス素子。 - 【請求項12】請求項1乃至11のいずれかに記載のエレ
クトロルミネセンス素子において、少なくとも第1と第
2の電荷キャリヤ注入接触層の一つは支持基板に接触し
ていることを特徴とするエレクトロルミネセンス素子。 - 【請求項13】請求項9記載のエレクトロルミネセンス
素子において、支持基板は石英ガラスからなることを特
徴とするエレクトロルミネセンス素子。 - 【請求項14】請求項1乃至13のいずれかに記載のエレ
クトロルミネセンス素子において、前記エレクトロルミ
ネセンス素子によってアレイを形成し、前記第1と第2
の電荷キャリヤ注入接触層が前記アレイに選択的にアド
レスすることを許容すべく配列されていることを特徴と
するエレクトロルミネセンス素子。 - 【請求項15】少なくとも一種の共役ポリマーからなる
緻密なポリマー膜の形状の半導体層を有し、ポリマー膜
として前駆体ポリマーの層を基板上に付着させる工程
と、前記付着された前駆体ポリマーを高温に加熱して共
役ポリマーに生成する工程と、第1の接触層の薄層を前
記半導体層の第1の表面と接して設け、第2の接触層の
薄層を前記半導体層の第2の表面と接して設ける工程と
からなり、前記ポリマー膜は、第2の接触層を第1の接
触層に対して正にするように前記半導体層の第1及び第
2の接触層間に電界をかけることにより電荷キャリヤが
前記半導体層に注入されて、前記半導体層から発光がな
される十分に低い濃度の外部電荷キャリヤを有し、さら
に前記共役ポリマーは発光色を制御する半導体バンドギ
ャップを有することを特徴とするエレクトロルミネセン
ス素子の製造方法。 - 【請求項16】請求項15記載の製造方法において、先
ず、支持基板上に前記第1の電荷注入接触層を付着させ
て複合基板を形成し、前記第1の電荷注入接触層上にポ
リマー膜として前記前駆体ポリマーを付着させ、次に複
合基板及び前駆体ポリマーをポリマー膜中に前記共役ポ
リマーを生成する高温に加熱し、最後に前記第2の電荷
注入接触層をポリマー膜上に設けることを特徴とするエ
レクトロルミネセンス素子の製造方法。 - 【請求項17】請求項15または16記載の製造方法におい
て、前駆体を構成するポリマーは可溶体で且つポリマー
膜としてスピンコーティングにより前記基板上に設けら
れることを特徴とするエレクトロルミネセンス素子の製
造方法。 - 【請求項18】請求項15乃至17のいずれかに記載の製造
方法において、 前記前駆体ポリマーはポリ(p−フェニレンビニレン)
[PPV]のための前駆体ポリマーであることを特徴とす
るエレクトロルミネセンス素子の製造方法。 - 【請求項19】請求項15乃至18のいずれかに記載の製造
方法において、前記ポリマー膜は10nmから5μmの範囲
において均一な厚さを有することを特徴とするエレクト
ロルミネセンス素子の製造方法。 - 【請求項20】請求項15乃至19のいずれかに記載の製造
方法において、第1の電荷キャリヤ注入接触層はアルミ
ニウムの薄い層からなり、一つの表面が薄い酸化層を形
成し、前記第1の電荷キャリヤ注入接触層の薄い酸化層
が前記半導体層の第1の表面と接触するよう設けられる
ことを特徴とするエレクトロルミネセンス素子の製造方
法。 - 【請求項21】請求項15乃至20のいずれかに記載の製造
方法において、前記第2の電荷キャリヤ注入接触層はア
ルミニウムと金からなるグループから選択されることを
特徴とするエレクトロルミネセンス素子の製造方法。 - 【請求項22】請求項15乃至19のいずれかに記載の製造
方法において、第1の接触層はアルミニウムとマグネシ
ウム/銀の合金からなるグループから選択され、且つ第
2の接触層は酸化インジウムであることを特徴とするエ
レクトロルミネセンス素子の製造方法。 - 【請求項23】請求項15乃至19のいずれかに記載の製造
方法において、前記第1の接触層はアモルファスシリコ
ンからなり、第2の接触層はアルミニウム、金、および
酸化インジウムからなるグループから選択されることを
特徴とするエレクトロルミネセンス素子の製造方法。 - 【請求項24】請求項15乃至23のいずれかに記載の製造
方法において、前記第1と第2の電荷キャリヤ注入接触
層は蒸着によって設けられることを特徴とするエレクト
ロルミネセンス素子の製造方法。 - 【請求項25】請求項15乃至24のいずれかに記載の製造
方法において、前記支持基板が石英ガラスであることを
特徴とするエレクトロルミネセンス素子の製造方法。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB898909011A GB8909011D0 (en) | 1989-04-20 | 1989-04-20 | Electroluminescent devices |
GB8909011.2 | 1989-04-20 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9116158A Division JPH1092576A (ja) | 1989-04-20 | 1997-04-18 | 電界発光素子およびその製造方法 |
JP11615997A Division JP3239991B2 (ja) | 1989-04-20 | 1997-04-18 | エレクトロルミネセンス装置およびその製造方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04500582A JPH04500582A (ja) | 1992-01-30 |
JP3249971B2 true JP3249971B2 (ja) | 2002-01-28 |
Family
ID=10655404
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP50602890A Expired - Lifetime JP3249971B2 (ja) | 1989-04-20 | 1990-04-18 | エレクトロルミネセント素子 |
JP9116158A Pending JPH1092576A (ja) | 1989-04-20 | 1997-04-18 | 電界発光素子およびその製造方法 |
JP11615997A Expired - Lifetime JP3239991B2 (ja) | 1989-04-20 | 1997-04-18 | エレクトロルミネセンス装置およびその製造方法 |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9116158A Pending JPH1092576A (ja) | 1989-04-20 | 1997-04-18 | 電界発光素子およびその製造方法 |
JP11615997A Expired - Lifetime JP3239991B2 (ja) | 1989-04-20 | 1997-04-18 | エレクトロルミネセンス装置およびその製造方法 |
Country Status (14)
Country | Link |
---|---|
US (2) | US5247190A (ja) |
EP (1) | EP0423283B1 (ja) |
JP (3) | JP3249971B2 (ja) |
KR (1) | KR100189398B1 (ja) |
AT (1) | ATE117834T1 (ja) |
AU (1) | AU626415B2 (ja) |
BR (1) | BR9006718A (ja) |
CA (1) | CA2030785C (ja) |
DE (1) | DE69016345T2 (ja) |
ES (1) | ES2070320T3 (ja) |
FI (1) | FI112555B (ja) |
GB (1) | GB8909011D0 (ja) |
HK (1) | HK24597A (ja) |
WO (1) | WO1990013148A1 (ja) |
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-
1989
- 1989-04-20 GB GB898909011A patent/GB8909011D0/en active Pending
-
1990
- 1990-04-18 KR KR1019900702649A patent/KR100189398B1/ko not_active IP Right Cessation
- 1990-04-18 JP JP50602890A patent/JP3249971B2/ja not_active Expired - Lifetime
- 1990-04-18 DE DE69016345T patent/DE69016345T2/de not_active Expired - Lifetime
- 1990-04-18 WO PCT/GB1990/000584 patent/WO1990013148A1/en active IP Right Grant
- 1990-04-18 EP EP90906272A patent/EP0423283B1/en not_active Expired - Lifetime
- 1990-04-18 BR BR909006718A patent/BR9006718A/pt not_active IP Right Cessation
- 1990-04-18 US US07/634,117 patent/US5247190A/en not_active Expired - Lifetime
- 1990-04-18 AT AT90906272T patent/ATE117834T1/de not_active IP Right Cessation
- 1990-04-18 AU AU54285/90A patent/AU626415B2/en not_active Expired
- 1990-04-18 CA CA002030785A patent/CA2030785C/en not_active Expired - Lifetime
- 1990-04-18 ES ES90906272T patent/ES2070320T3/es not_active Expired - Lifetime
- 1990-12-19 FI FI906271A patent/FI112555B/fi active IP Right Grant
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1993
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1997
- 1997-02-27 HK HK24597A patent/HK24597A/xx not_active IP Right Cessation
- 1997-04-18 JP JP9116158A patent/JPH1092576A/ja active Pending
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FI112555B (fi) | 2003-12-15 |
ES2070320T3 (es) | 1995-06-01 |
CA2030785C (en) | 2000-05-30 |
EP0423283B1 (en) | 1995-01-25 |
DE69016345D1 (de) | 1995-03-09 |
CA2030785A1 (en) | 1990-10-21 |
JP3239991B2 (ja) | 2001-12-17 |
EP0423283A1 (en) | 1991-04-24 |
HK24597A (en) | 1997-02-27 |
US5399502A (en) | 1995-03-21 |
JPH1092577A (ja) | 1998-04-10 |
AU5428590A (en) | 1990-11-16 |
US5247190A (en) | 1993-09-21 |
AU626415B2 (en) | 1992-07-30 |
KR100189398B1 (ko) | 1999-08-02 |
JPH1092576A (ja) | 1998-04-10 |
DE69016345T2 (de) | 1995-05-24 |
KR920700480A (ko) | 1992-02-19 |
BR9006718A (pt) | 1991-08-06 |
JPH04500582A (ja) | 1992-01-30 |
GB8909011D0 (en) | 1989-06-07 |
WO1990013148A1 (en) | 1990-11-01 |
FI906271A0 (fi) | 1990-12-19 |
ATE117834T1 (de) | 1995-02-15 |
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