TWI255665B - Organic electroluminescent device - Google Patents
Organic electroluminescent device Download PDFInfo
- Publication number
- TWI255665B TWI255665B TW093129006A TW93129006A TWI255665B TW I255665 B TWI255665 B TW I255665B TW 093129006 A TW093129006 A TW 093129006A TW 93129006 A TW93129006 A TW 93129006A TW I255665 B TWI255665 B TW I255665B
- Authority
- TW
- Taiwan
- Prior art keywords
- layer
- organic
- layers
- glass transition
- transition temperature
- Prior art date
Links
- 239000010410 layer Substances 0.000 claims abstract description 129
- 239000002346 layers by function Substances 0.000 claims abstract description 28
- 230000009477 glass transition Effects 0.000 claims abstract description 24
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 15
- 239000010409 thin film Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 39
- 238000002347 injection Methods 0.000 description 20
- 239000007924 injection Substances 0.000 description 20
- 230000005525 hole transport Effects 0.000 description 18
- 230000032258 transport Effects 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- -1 naphthyl cyanine derivative Chemical class 0.000 description 10
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 4
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 3
- 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 3
- 150000000183 1,3-benzoxazoles Chemical class 0.000 description 2
- 241000234282 Allium Species 0.000 description 2
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BGZVBIAMRYGGSS-UHFFFAOYSA-N 1,1,2-triphenylhydrazine Chemical class C=1C=CC=CC=1NN(C=1C=CC=CC=1)C1=CC=CC=C1 BGZVBIAMRYGGSS-UHFFFAOYSA-N 0.000 description 1
- NOIXUZSKNIAJKZ-UHFFFAOYSA-N 1-benzhydrylpyridin-1-ium Chemical class C1=CC=CC=C1C([N+]=1C=CC=CC=1)C1=CC=CC=C1 NOIXUZSKNIAJKZ-UHFFFAOYSA-N 0.000 description 1
- RWJXYKRBXKAWQG-UHFFFAOYSA-N CC12CC=C(N1)C=C1C=CC(C=C3C=CC(=CC=4C(=CC(=C2)N4)O)N3)=N1 Chemical compound CC12CC=C(N1)C=C1C=CC(C=C3C=CC(=CC=4C(=CC(=C2)N4)O)N3)=N1 RWJXYKRBXKAWQG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 244000273256 Phragmites communis Species 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- AXTYOFUMVKNMLR-UHFFFAOYSA-N dioxobismuth Chemical compound O=[Bi]=O AXTYOFUMVKNMLR-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000008376 fluorenones Chemical class 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 description 1
- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 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
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 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
-
- 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
- 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
- H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/186—Metal complexes of the light metals other than alkali metals and alkaline earth metals, i.e. Be, Al or Mg
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
-
- 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
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
-
- 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
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
-
- 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
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- 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
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Description
1255665 九、發明說明:
L發明戶斤屬之技術領域I 發明領域 本發明係有關於一種有機電致發光裝置(其後稱為有 5 機EL裝置),其具有一或多個薄膜(其後稱為有機功能性 層),其包含發光層。發光層係由顯示電致發光性之有機化 合物製成,其間,光係藉由施加電流而發射。 I:先前技術】 相關技藝描述 10 有機EL裝置基本上包含一含有發光層之有機功能性 層,及正電極(其係顯示電極)及負電極,有機功能性層係被 夾置於其間。當自二電極發射之電子及電洞(正電洞)被再次 結合時,激子產生。當激子自激發態回到基態時,光被發 射。有機EL裝置包含,例如,一透明正電極、一有機功能 15 性層,及一金屬負電極,其等係被連續層合於透明基材上。 有機功能性層包含多數個具有同功能之層,例如,電洞注 射層、電洞運送層,發光層、電子運送層,及電子注射層, 其等係以此順序自透明電極側層合。電洞注射層及電洞運 送層係由具有運送電洞功能之材料製成,且電子運送層及 20 電子注射層係由具有運送電子功能之材料製成。除發光層 外之此等層被稱為電荷運送層。電荷運送層增加電荷注射 於發光層内之效率,因此,與僅包含發光層之裝置相比顯 著地改良發光效率。實際上,某些有機EL裝置不具有此一 電荷運送層,且有些有機EL裝置具有多數個電荷運送層。 1255665 再者,發光層可包含多數個層,例如,如同具有二發光層 (即,發射藍光之層及發射紅光之層)之發射白光之裝置。 【發明内容】 發明概要 5 傳統上,具有由於有機功能性層之材料隨時間消逝之 往復作用及耐用性而產生未展現出所欲發射之顏色的問 題。 本發明目的係提供一種具高可靠性之有機EL裝置。 依據本發明之有機EL裝置係一種有機電致發光裝置, 10 其包含一對彼此相對之正及負的電極間,及一有機功能性 層,其係形成於正及負電極且具有三或更多之薄膜,包含 一由有機化合物製得之發光層。有機功能性層包含一對第 一及第二層,及一被維持於第一及第二層間之第三層。第 一及第二層之每一者係由玻璃轉移溫度係等於或高於第一 15 溫度之有機化合物製成,且第三層係由玻璃轉移溫度係低 於第一溫度之有機化合物製成。第三層具有30 nm或更少之 厚度。 圖式簡單說明 第1圖係顯示依據本發明一實施例之有機EL裝置之結 20 構之圖。 第2圖係顯示依據本發明另一實施例之有機EL裝置之 結構之圖。
L實施方式H 發明詳細說明 1255665 若有機EL裝置之有機功能性層中之彼此相鄰之二芦皆 由具破璃轉移溫度(τ§)之材料製成,則發光性降解、I产 降解等會於此裝置被置於高溫環境時發生。基於此狀況; 各種原型之有機既裝置被製造及評估。每_有機虹裝置星 5有一有機功能性層,其間,由具低玻璃轉移溫度之材料f 成之層被夾置於由具高坡_移溫度之材料製成之層間。 ^此’电現右夾置層及被失置之層間之玻簡移溫度差(= 同玻璃轉移温度_低玻壤轉移溫度)不足時,發光性降解係發 生於此裝置被維持於熱環境—段長時間時。 x 10、對於有機EL裝置之有機功能性層,其係難以自具足夠 南之玻璃轉移溫度之材料選擇具有對此裝置之連續趨動具 良好对用!生或於發光具良好趨動效率之材料。依據本發 明,有機功能性層内之厚度的決定擴大其材料之選擇。 本發明之一實施例將於其後參考圖式描述。 15 如第1圖所示之依據本發明之有機EL裝置包含一透明 正電極2、一有機功能性層3,及一金屬負電極4,其等被連 續層合於一由,例如,玻璃、塑膠等製成之透明基材丨上。 光係自透明基材1之側發射。為使光發射出,正及負電極之 至少一者需為透明或半透明。由有機化合物製成之有機功 2〇能性層3包含多數層。此多數層之每一者具有一功能,例 如,電洞注射層30、電洞運送層31、發光層32,及電子運 送層33 ’其係如苐1圖所示自透明電極2之側層合。此外, 如第2圖所示,有機功能性層3玎被建構成電洞注射層3〇/第 —電洞運送層3 la/第二電洞運送層31 b/發光層32/電子運送 1255665 層33之堆疊物,其等係自透明電松之靜人+ 34可被設於電子料層 s ° ° $子注射層 ,、孟屬電極4之間,以秘丄+ 7 射效率。發光層及電荷運 3加电子注 ,Ρ — 層(邊如,電洞運送屑另+工、富 送層)之母-者可由多數層組成。 …子運 屬氧化物、導電化合物,及其等之混 …口至、金 函數等於或高於4eV之材料。正^°。較佳係使用功 物στο)、以銻捭^ 电 由,例如,銦錫氧化 物(_以㈣奴氣化錫()、 10 15 20 _、半導性金屬氧化物(氧化錫、氧化辞、=化: 鋅氧化物(ΙΖ0)等)、金屬(金、銀、鉻 飞匕扣、銦 性全屬气外私^、日人t 、呆寺)、此金屬及導 =心'域導崎咖匕銅、 肌化銅寺)、有機¥性材料(聚苯胺、聚π塞吩 、 有機導性材料及ΓΓ0之層合物等製成。正電極、合 如,於ϊτο之情況係約1000至3〇〇11111,且 又糸’例 ? 1sn /e e 、至之情況係約800 = /111°〜,正電極厚度可依據材__«_ 而適當選擇。 处价千 金屬電極愤有作為貞電極之魏,叫電子注射 機功能性層内。用於負電極之材料之例子包含全屬、人全、 金屬氧化物、導電化合物,及其等之屍合物。較佳地口,此 金屬電極係由具低電阻之材料製成,諸如, 4呂。另外,諸 ㈣合金或其等之以物之合金可被使 以曰代使用銘。為增加電子注射於有機功能性層内 .,具約數埃厚度且由UF(氟化鍾)、U2〇(氧化链)、 1255665
Cs·化铯)等製成之電付射層3何被插人。較佳地,盘 有機功能性層金屬電極及電子㈣層《功函數等 H⑽4‘5&_製成。例如’驗金屬叫,Na,κ,&等) 或驗土金屬(Mg,Ca等)可被添加至此等材料。此等材料可單 獨使用,但較佳係使二或更多種材料_起使用,以獲得安 定性及注射電子之功能。 /友據本發明實施例之有機EL裝置包含有機功能性層, 爲係开/成於纽相狀—對正及貞電極之間。有機功能性 ^ G 5二或更多個薄膜,其包含由有機化合物製成之發光 層、。,有機功能性層包含—對第—及第二層(例如,第一電洞 運I層31a及發光層32),及一第三層⑽如,第二電洞運送 ㈣的其係維持於第一及第二層之間。第—及第二層之每 者係由破璃轉移溫度係等於或高於第-溫度(例如,98。〇 声有機化合物製成。第三層係由玻璃轉移溫度低於第一溫 有機化合物製成。第三層係形成具有30 mn或更少之厚 度。 對於依據本發明實施例之有機£1裝置,其結構可定為 相鄰之箪=& . 声、〃 一 g及第一及第二層之至少一者間之玻璃轉移溫 X差係等於或多於18t之方式。用於第一、 之材料r4 人木一/曰 、’、糸k自具有前述玻璃轉移溫度關係之材料。此係因 2毛光性降解不會發生,即使有機EL裝置被維持於高溫環 長T間’只要有機EL裝置包含具有30 nm或更少厚度 ^ 且第三層及第一或第二層間之玻璃轉移溫度差 少於18。(:。 1255665 玻璃轉移溫度指示有機化合物之熱安定性。玻璃轉移 溫度愈高,非結晶性薄膜變得更具熱安定性。若第一溫度 係作為標準之98°C,如本實施例,可獲得因熱安定性而具 長時間能量化作用之安定的光發射。考量於高溫條件下之 5 操作環境等,某一程度之功效可被預期,即使於第一溫度 等於或高於110°C時。本實施例採用藉由差式掃瞄量熱計測 得之數值。 被夾置之第三層可為電洞注射層、發光層、電子運送 層,或電子注射層,以替代電洞運送層,只要第三層之玻 10 璃轉移溫度低於夾置之第一及第二層者。 電洞運送材料(其作為依據本發明實施例之有機EL裝 置之電洞注射層及電洞運送層)係選自具有除前述條件外 另具有運送電洞及注射電洞之功能且可避免電子移入電洞 運送層内(若可能時)之化合物。電洞運送材料之例子包含酞 15 菁配位基衍生物、萘菁基衍生物、卟啉衍生物、芳香族二 胺衍生物,諸如,4,4’-雙[N-(萘基苯基-胺基]聯苯 (α-NPD),及胺化合物。 依據本發明實施例之有機EL裝置内之發光層之宿主材 料之例子包含縮合之多環衍生物,諸如,蔥、祐、并四苯、 20 暈苯、二萘嵌苯、酞二萘嵌苯,及萘二萘嵌苯;及喳啉酚 金屬錯合物,諸如,三(8-羥基喳啉酚基)鋁、三(4-甲基-8-嗉啉酚基)鋁、三(5-苯基-8·嗉啉酚基)鋁,及雙(4-曱基-8-°秦°林酴基)铭。例如,以下述化學式(1)表示之BAlq(Th=99 °C )、以下述化學式(2)表示之宿主(Tg二life),或以如下化 10 1255665 學式(3)表示之BEM-B(Tg=130°C )被作為有機發光層之宿主 材料。
用於發光層之掺雜材料之例子包含螢光材料,諸如, 5 香豆素化合物、唆σ丫酮化合物,及史提胺(stilamine),及石舞 光材料,諸如,配位基係苯基吡啶、乙醯基丙酮等之銥錯 合物◦例如,以如下所述化學式(4)表示之ΒφΙτ、以如下所 1255665 述化學式(5)表示之FIpic或以如下所述化學式(6)表示之 lr(ppy)3被作為用於有機發光層之摻雜材料。
5 作為依據本發明實施例之有機EL裝置中之電子運送層 之電子運送材料係選自除前述條件外另具有運送電子及注 射電子之功能且可避免電洞移入電子運送層内(若可能)之 化合物。電子運送材料之例子包含三σ坐衍生物、σ惡峻衍生 物、σ惡二°坐衍生物、苟酮衍生物、蔥S昆-曱烧衍生物、安塞 12 1255665 酮(anthorone)衍生物、二苯基苯醌衍生物、。塞。比喃二氧化物 少亍生物、石反一酸亞胺衍生物、苟叉基甲垸衍生物、二苯甲 基吡嗉衍生物、雜環四羧酸酐,諸如,萘二萘嵌苯、金屬 錯合物,諸如,酞菁配位基衍生物及喳琳紛衍生物,配位 5基係金屬酞菁配位基、苯并噁唑、苯并嘍唑等之金屬錯合 物、笨胺共聚物、導性聚合物,諸如,嚷吩寡聚物及聚嗔 吩、聚噻吩衍生物、聚苯撐衍生物、聚苯撐乙烯撐衍生物, 及聚芴衍生物。 [實施例] 10 具體地,多數個有機EL裝置之樣品被製造以評估發光 特性。 於每一樣品,下列材料被連續沈積於位於一基材上之 IT0正電極(厚度:11Qnm)上,以製得具有下列結構之有機 EL裝置。 15 每一有機功能性層係如第1圖所示藉由使用酞菁酮 (CuPc)(個別厚度:25 nm)用於電洞注射層,htm_A(個別厚 度· 45nm,30nm,15nm,0nm)用於電洞運送層,α·ΝρΕ)(個 又nm’ 25 nm,40 nm,55 nm)用於第二電洞運送 層,以BtpIr為摻雜材料以BAlq為宿主材料(厚度:475nm) 用於I光層,Alq3(個別厚度:3〇 nm)用於電子運送層。電 洞庄射材料之CuPc係熱安定性,且其玻璃轉移溫度及溶點 於齡析中皆未被觀察到高達3〇〇t:。HTM-A係破璃轉移溫 度係12〇t之電洞運送材料。發光層之BAlq具有99。(:之玻璃 心私概度。ΒψΙτ係磷光摻雜劑。作為電子運送材料之Alq3 13 1255665 具有167°C之玻璃轉移溫度。 然後,於每一樣品,LiF於電子運送層上蒸發作為電子 注射層以具有1 nm之厚度。再者,鋁(A1)被層合於其上作為 負電極,其具有1〇〇 nm之厚度,以製得此實施例之有機發 5 光裝置之樣品。 第1表顯示實施例1至4之有機功能性層之厚度狀態。 第1表 樣 有機功能性層之厚度(nm) 品 CuPc(Tg=>300 HTM-A(Tg=120 a-NPD(Tg=96 BAlq(Tg=99 Alq3(Tg=167 °C) °C) °C) °C)+Btplr °C) 1 25 45 10 47.5 30 2 25 30 25 47.5 30 3 25 15 40 47.5 30 4 25 0 55 47.5 30 有機EL裝置之樣品被保持於100°c恆溫箱内一段預定 時間(小時)。第2表顯示當此等裝置其後以5.5 mA/cm2趨動 10 時之此等裝置之色度及發光效率(cd/A)變化。 第2表 樣品 電洞運送層: 厚度 100°C時之消逝 時間(小時) 色度 發光效率 (cd/A) CDEx CEy 1 HTM-A:45nm a-NPD: lOnm 0 0.679 0.321 6.3 20 0.677 0.322 6.3 80 0.674 0.325 6.6 150 0.670 0.328 5.5 2 HTM-A:30nm a-NPD:25nm 0 0.678 0.321 6.4 20 0.679 0.321 6.3 80 0.673 0.325 6.2 150 0.659 0.334 3.6 3 HTM-A:15nm a-NPD:40nm 0 0.677 0.321 6.3 20 0.678 0.321 6.3 80 0.673 0.325 5.6 150 0.643 0.345 2.2 4 HTM-A:Onin a-NPD:55nm 0 0.678 0.321 6.5 20 0.678 0.321 6.3 80 0.674 0.324 5.0 150 0.605 0.369 1.3 由第2表明顯地,於裝置樣品1及2,色度未改變且發光 效率未降低一半,即使於此等裝置被保持於100°C:之恆溫箱 1255665 内150小時後。與其等相比較,於比較裝置3及4中,其色度 產生重大變化且發光效率降低一半。於本實施例,Htm-A 層(120 C之玻璃轉移溫度)被以使(x—npd層變薄之方式沈積 於CuPc層及α-NPD層之間。此外,熱安定之CuPc層可被形 5 成為厚的且α-NPD層為薄。 作為另外經驗,有機EL裝置樣品5及6以相似於上述實 施例之方式製造,但厚度係如下第3表所示,且前述具有113
C玻璃轉移溫度之宿主被作為發光層之宿主材料以替代 BAlq 〇 10 第3表 樣 有機功能性層之厚唐' 品 CuPc(T»=>300 °〇 。 HTM-A(Tg=120 °〇 a-NPD(Tg=96 °〇 宿主(Tg=113 °C)-f Btplr Alq3(Tg=167〜" °C) 5 25 30 25 40 37.5'〜 6 25 0 55 40 37.5^^^ 前述裝置樣品個別被保持於100 °c恆溫箱内一段預定 時間(小時)。第4表顯示當此等裝置其後以5.5 mA/cm2趨動 時之此等裝置之色度及發光效率(cd/A)變化。 第4表 樣品 電洞運送 層:厚度 KX)°C時之消逝 時間(小時) _ 色度 發光 (cd/A) CIEx CEEy 5 HTM-A:30nm a-NPD:25nm 0 0.680 03Ϊ9 6.6^— 150 0.678 0.321 300 0.674 0.323 6.2^— 500 0.673 0.324 5.9^^ 6 HTM-A:0nm a-NPD:55nm 0 0.678 0.320 6·4^^ 150 0.675 0.323 5·4、^ 300 0.675 0.323 5.0、·— 500 0.672 0.326 3.6^^
笫4表明顯地,裝置樣品5之實施列之發光效率僅減少 10%,即使於此等裝置被保持於l〇〇°C之恆溫箱内500小時 後。於裝置樣品6之比較例,與其等相比較,發光效率於保 15 1255665 存500小時後減少44%。 因為有機EL裝置係以本發明實施例之方式建構,諸如 發光性降解及色度改變之問題不會發生,即使此裝置被保 持於高溫環境。再者,具有材料之選擇變容易之功效。特 5 別地,以置放於交通工具上為前提,應用本發明改良產品 可靠性。 I:圖式簡單說明3
第1圖係顯示依據本發明一實施例之有機EL裝置之結 構之圖。 10 第2圖係顯示依據本發明另一實施例之有機EL裝置之 結構之圖。
【主要元件符號說明】 1…·, ..透明基材 31b.. .....第二電洞i 2 ..透明正電極 32... ...發光層 3····. ..有機功能性層 33... ...電子運送層 30... ...電洞注射層 34... ...電子注射層 31... ...電洞運送層 4·.··. ..金屬負電極 31a.. .....第一電洞運送層 16
Claims (1)
1255665 十、申請專利範圍: 1. 一種有機電致發光裝置,其包含:一對彼此相對之正及 負之電極;及一有機功能性層,其係於該正及負之電極間 形成且具有三或更多個薄膜層,其包含一由有機化合物製 5 得之發光層,其特徵在於該有機功能性層包含一對第一及 第二層,及一被維持於該第一及第二層間之第三層,該第 一及第二層之每一者係由玻璃轉移溫度係等於或高於第一 溫度之有機化合物製成,該第三層係由玻璃轉移溫度係低 於該第一溫度之有機化合物製成,且該第三層具有30 nm或 10 更少之厚度。 2. 如申請專利範圍第1項之有機電致發光裝置,其中,該第 三層之該玻璃轉移溫度係於滿足該第三層及該第一或第二 層間之玻璃轉移溫度差係少於18t之範圍内。 3. 如申請專利範圍第1或2項之有機電致發光裝置,其中, 15 該第一溫度係98°C。 4. 如申請專利範圍第1項之有機電致發光裝置,其中,該第 三層係由具有運送電洞功能之材料製成。 17
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