TWI498044B - Organic light emitting device - Google Patents
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- TWI498044B TWI498044B TW097144811A TW97144811A TWI498044B TW I498044 B TWI498044 B TW I498044B TW 097144811 A TW097144811 A TW 097144811A TW 97144811 A TW97144811 A TW 97144811A TW I498044 B TWI498044 B TW I498044B
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- 239000000463 material Substances 0.000 claims description 159
- 230000005525 hole transport Effects 0.000 claims description 45
- 229910052723 transition metal Inorganic materials 0.000 claims description 29
- 150000003624 transition metals Chemical class 0.000 claims description 29
- -1 triazine compound Chemical class 0.000 claims description 18
- 238000004770 highest occupied molecular orbital Methods 0.000 claims description 12
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 claims description 10
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 claims description 10
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 claims description 10
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- SSABEFIRGJISFH-UHFFFAOYSA-N 2-(2,4-difluorophenyl)pyridine Chemical compound FC1=CC(F)=CC=C1C1=CC=CC=N1 SSABEFIRGJISFH-UHFFFAOYSA-N 0.000 claims description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 6
- LTUJKAYZIMMJEP-UHFFFAOYSA-N 9-[4-(4-carbazol-9-yl-2-methylphenyl)-3-methylphenyl]carbazole Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C(=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C)C(C)=C1 LTUJKAYZIMMJEP-UHFFFAOYSA-N 0.000 claims description 5
- UTLXNDJBWUGIIF-UHFFFAOYSA-N C1=CC=CC=C1C1(C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC=CC=2)C=2C=CC(=CC=2)C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC=CC=2)C2=CC=CC=C2C2=CC=CC=C21 Chemical compound C1=CC=CC=C1C1(C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC=CC=2)C=2C=CC(=CC=2)C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC=CC=2)C2=CC=CC=C2C2=CC=CC=C21 UTLXNDJBWUGIIF-UHFFFAOYSA-N 0.000 claims description 5
- 229910016460 CzSi Inorganic materials 0.000 claims description 5
- WIHKEPSYODOQJR-UHFFFAOYSA-N [9-(4-tert-butylphenyl)-6-triphenylsilylcarbazol-3-yl]-triphenylsilane Chemical compound C1=CC(C(C)(C)C)=CC=C1N1C2=CC=C([Si](C=3C=CC=CC=3)(C=3C=CC=CC=3)C=3C=CC=CC=3)C=C2C2=CC([Si](C=3C=CC=CC=3)(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=C21 WIHKEPSYODOQJR-UHFFFAOYSA-N 0.000 claims description 5
- 150000001491 aromatic compounds Chemical class 0.000 claims description 5
- 150000003512 tertiary amines Chemical class 0.000 claims description 5
- HSTCJLDQVIIDKF-UHFFFAOYSA-N 1-phenyldecylbenzene Chemical compound C=1C=CC=CC=1C(CCCCCCCCC)C1=CC=CC=C1 HSTCJLDQVIIDKF-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- UKYDTINMKPJTQD-UHFFFAOYSA-N 1-[4-[2-[2-[4-(9h-carbazol-1-yl)phenyl]phenyl]phenyl]phenyl]-9h-carbazole Chemical group C12=CC=CC=C2NC2=C1C=CC=C2C(C=C1)=CC=C1C1=CC=CC=C1C1=CC=CC=C1C1=CC=C(C=2C=3NC4=CC=CC=C4C=3C=CC=2)C=C1 UKYDTINMKPJTQD-UHFFFAOYSA-N 0.000 claims description 3
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- GWFGARXUJNKOMY-UHFFFAOYSA-N [3,5-di(carbazol-9-yl)phenyl]-triphenylsilane Chemical compound C1=CC=CC=C1[Si](C=1C=C(C=C(C=1)N1C2=CC=CC=C2C2=CC=CC=C21)N1C2=CC=CC=C2C2=CC=CC=C21)(C=1C=CC=CC=1)C1=CC=CC=C1 GWFGARXUJNKOMY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
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- 150000002148 esters Chemical class 0.000 claims description 3
- BPEVHDGLPIIAGH-UHFFFAOYSA-N ruthenium(3+) Chemical compound [Ru+3] BPEVHDGLPIIAGH-UHFFFAOYSA-N 0.000 claims description 3
- 125000004890 (C1-C6) alkylamino group Chemical group 0.000 claims description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 5
- GLWVSYKBNMXDPS-UHFFFAOYSA-N (8-diphenylphosphanyldibenzofuran-2-yl)-diphenylphosphane Chemical compound C1=CC=CC=C1P(C=1C=C2C3=CC(=CC=C3OC2=CC=1)P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 GLWVSYKBNMXDPS-UHFFFAOYSA-N 0.000 claims 2
- DWYHDSLIWMUSOO-UHFFFAOYSA-N 2-phenyl-1h-benzimidazole Chemical group C1=CC=CC=C1C1=NC2=CC=CC=C2N1 DWYHDSLIWMUSOO-UHFFFAOYSA-N 0.000 claims 2
- FVKUPLOUKKINTI-UHFFFAOYSA-N C1=CC=NC(=C1)C2=NC(NN=C2)(C(F)(F)F)O Chemical compound C1=CC=NC(=C1)C2=NC(NN=C2)(C(F)(F)F)O FVKUPLOUKKINTI-UHFFFAOYSA-N 0.000 claims 2
- RQMOPRSKAURTHH-UHFFFAOYSA-N [Ru].FC1=C(C=CC(=C1)F)C1=NC=CC=C1.FC1=C(C=CC(=C1)F)C1=NC=CC=C1 Chemical compound [Ru].FC1=C(C=CC(=C1)F)C1=NC=CC=C1.FC1=C(C=CC(=C1)F)C1=NC=CC=C1 RQMOPRSKAURTHH-UHFFFAOYSA-N 0.000 claims 2
- PEIXNURIXNGPQG-UHFFFAOYSA-N dibenzothiophen-1-yl(diphenyl)phosphane Chemical compound C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=2SC3=C(C=21)C=CC=C3 PEIXNURIXNGPQG-UHFFFAOYSA-N 0.000 claims 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 claims 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims 2
- 229920001296 polysiloxane Polymers 0.000 claims 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 claims 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 4
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
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- DIOURSRLPLXSNY-UHFFFAOYSA-N 2-[3,5-bis(4-phenyl-1h-benzimidazol-2-yl)phenyl]-4-phenyl-1h-benzimidazole Chemical compound C1=CC=CC=C1C1=CC=CC2=C1NC(C=1C=C(C=C(C=1)C=1NC3=C(C=4C=CC=CC=4)C=CC=C3N=1)C=1NC3=C(C=4C=CC=CC=4)C=CC=C3N=1)=N2 DIOURSRLPLXSNY-UHFFFAOYSA-N 0.000 description 1
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- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
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- CELAVSIYCCQNGG-UHFFFAOYSA-N n-(4-cyclohexylphenyl)-4-methyl-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1CCCCC1)C1=CC=C(C)C=C1 CELAVSIYCCQNGG-UHFFFAOYSA-N 0.000 description 1
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- Electroluminescent Light Sources (AREA)
Description
本發明係有關於一種有機電激發光元件，特別是一種具有雙層發光層之磷光有機電激發光元件，降低元件操作電壓與提高發光效率。The present invention relates to an organic electroluminescent device, and more particularly to a phosphorescent organic electroluminescent device having a double-layered light-emitting layer, which reduces the operating voltage of the device and improves the luminous efficiency.
近年來平面顯示器已逐漸成為顯示器的主流，因此，有機電激發光元件隨之發展。In recent years, flat panel displays have gradually become the mainstream of displays, and as a result, organic electroluminescent elements have been developed.
有機電激發光元件之發光原理為，一有機半導體薄膜元件，在外加電場作用的情況下，電子與電洞分別由陰極電極與陽極電極注入，並且在此元件中進行傳遞。當電子與電洞在有機發光層中相遇後，電子與電洞會再結合(recombination)而形成一激發子(exciton)，而激發子會在電場作用下將能量傳遞給有機發光層中的發光分子，進而激發發光分子，接著，受激發的發光分子便將能量以光的形式釋放出能量。一般的有機電激發光元件係在陽極電極(例如銦錫氧化物)上蒸鍍一層電洞傳輸層(hole－transporting layer)，接著，於其上蒸鍍一層有機發光層(organic emitting layer)，再蒸鍍電子傳輸層(electron－transporting layer)，最後，在於電子傳輸層上蒸鍍金屬，以作為陰極電極。簡單來說，就是一種由電生光的裝置。The principle of illumination of an organic electroluminescent device is an organic semiconductor thin film element. In the case of an applied electric field, electrons and holes are respectively injected from the cathode electrode and the anode electrode, and are transferred in the element. When electrons and holes meet in the organic light-emitting layer, electrons and holes recombination to form an exciton, and the excitons transfer energy to the organic light-emitting layer under the action of an electric field. The molecules, in turn, excite the luminescent molecules, and then the excited luminescent molecules release energy in the form of light. A general organic electroluminescent device evaporates a hole-transporting layer on an anode electrode (for example, indium tin oxide), and then evaporates an organic radiant layer thereon. An electron-transporting layer is further evaporated, and finally, a metal is vapor-deposited on the electron transport layer to serve as a cathode electrode. Simply put, it is a device that produces electricity from electricity.
而有機電激發光元件的發光顏色主要係取決於元件內具有螢光特性的有機材料，因此，一般有機發光層係在 主發光體(host)中混入少量的高發光效率之客發光體(guest)，來提高載子的再結合效率和元件發光效率。其中，客發光體若係以過渡金屬有機錯合物所組成，可藉由過渡金屬產生重原子效應，使三重態能量可以磷光方式緩解回基態。因此，由過渡金屬有機錯合物為客發光體與主發光體所組成之有機電激發光元件(亦稱為磷光有機電激發光元件)，該元件可以完全利用單重態(25%)與三重態(75%)之所有激發子來發光，與使用不含過渡金屬有機物為客發光體之有機電激發光元件(亦稱為螢光有機電激發光元件)相較，磷光有機電激發光元件可提高其內部量子效率達4倍。The color of the organic electroluminescent device depends mainly on the organic material having fluorescent properties in the device. Therefore, the general organic light-emitting layer is A small amount of high luminous efficiency guest light is mixed into the main illuminator to improve the recombination efficiency of the carrier and the luminous efficiency of the element. Wherein, if the guest illuminant is composed of a transition metal organic complex, the heavy atom effect can be generated by the transition metal, so that the triplet energy can be light-reduced to the ground state. Therefore, the transition metal-organic complex is an organic electroluminescent device (also referred to as a phosphorescent organic electroluminescent device) composed of a guest emitter and a main emitter, and the component can completely utilize singlet state (25%) and triple weight. All of the excitons of the state (75%) emit light, and the phosphorescent organic electroluminescent element is compared with an organic electroluminescent element (also referred to as a fluorescent organic electroluminescent element) that does not contain a transition metal organic substance as a guest emitter. It can increase its internal quantum efficiency by a factor of four.
在磷光有機電激發光元件中，有機發光層的材料組成為一重要的關鍵。為了避免能量轉移或回傳到三重態較低的有機物上，通常主發光體之三重態能階必須大於磷光客發光體材料(參考Ref.Appl.Phys.Lett. ,83 ,569(2003))。特別是在藍光磷光有機電激發光元件中，由於發藍光之磷光客發光體材料，其三重態能階約為2.7 eV，因此，需選用三重態能階大於2.7 eV的有機材料作為主發光體。然而，當有機分子所需的三重態能階越大，其單重態能階則越大。所以，一般來說，用於藍光磷光有機電激發光元件中之主發光體，其能帶(bandgap)皆大於3.0 eV。以如此大能帶的有機材料為主發光體製作成發光層，會與相鄰的電洞傳輸層或是電子傳輸層間，亦或是與兩者間，產生電荷傳輸的障礙。導致藍光磷光有機電激發光元 件，有高操作電壓及低發光效率的問題。In the phosphorescent organic electroluminescent device, the material composition of the organic light-emitting layer is an important key. In order to avoid energy transfer or return to the triplet organic matter, the triplet energy level of the primary illuminant must be greater than that of the phosphorescent illuminant material (Ref. Appl. Phys. Lett. , 83 , 569 (2003)) . Especially in the blue phosphorescent organic electroluminescent device, the triplet energy level of the blue light-emitting phosphorescent luminescent material is about 2.7 eV. Therefore, an organic material having a triplet energy level greater than 2.7 eV is required as the main illuminant. . However, the larger the triplet energy level required for an organic molecule, the larger its singlet energy level. Therefore, in general, the main illuminant used in the blue phosphorescent organic electroluminescent device has a bandgap greater than 3.0 eV. The organic material with such a large band can be used as the light-emitting layer to form a light-emitting layer, which may cause an obstacle to charge transfer between the adjacent hole transport layer or the electron transport layer or between the two. The blue phosphorescent organic electroluminescent device is caused to have a problem of high operating voltage and low luminous efficiency.
美國專利案第6,867,538號已揭露以相同於元件中所使用之電洞傳輸層材料為主發光體，並摻雜磷光客發光體材料作為發光層、及以相同於元件中所使用之電子傳輸層材料為主發光體，並摻雜磷光客發光體材料作為發光層，形成雙層發光層之有機電激發光元件，能克服載子由電洞或電子傳輸層傳遞至發光層的能障。然而，其中並未詳述各材料之間最高能量的電子填入分子軌域(Highest occupied molecular orbital,HOMO)及最低能量的電子未填入分子軌域(Lowest unoccupied molecular orbital,LUMO)對於元件效率之影響，和以電洞傳輸層和電子傳輸層材料作為主發光體時，其三重態能階對於元件效率之影響。U.S. Patent No. 6,867,538 discloses a hole-emitting layer material similar to that used in an element as a main light-emitting body, and is doped with a phosphorescent guest material as a light-emitting layer and the same electron transport layer used in the element. The material is a main illuminant, and the phosphorescent guest illuminant material is doped as a luminescent layer to form an organic electroluminescent element of the double luminescent layer, which can overcome the energy transfer of the carrier from the hole or the electron transport layer to the luminescent layer. However, there is no detailed description of the highest energy of the material between the materials (Highest occupied molecular orbital (HOMO) and the lowest energy of the unoccupied molecular orbital (LUMO) for component efficiency. The influence of the triplet energy level on the efficiency of the component when the hole transport layer and the electron transport layer material are used as the main illuminants.
因此，該如何降低元件之操作電壓，且能同時提高發光效率，是目前相關領域的技術人員亟欲克服的問題。Therefore, how to reduce the operating voltage of the component and simultaneously improve the luminous efficiency is a problem that those skilled in the related art are eager to overcome.
有鑑於上述問題，本發明之目的在於提供一種有機電激發光元件。In view of the above problems, it is an object of the invention to provide an organic electroluminescent device.
本發明之另一目的係提供一種能降低操作電壓與提高發光效率之磷光有機電激發光元件。Another object of the present invention is to provide a phosphorescent organic electroluminescent device capable of reducing an operating voltage and improving luminous efficiency.
為達上揭及其他目的，本發明係提供一種有機電激發光元件，包括：陽極；形成於陽極上之電洞傳輸層；形成於該電洞傳輸層上之第一發光層，使該電洞傳輸層夾置於該陽極和第一發光層之間，該第一發光層包括第一主發光 材料及過渡金屬有機錯合物；形成於該第一發光層上之第二發光層，使該第一發光層夾置於該電洞傳輸層和該第二發光層之間，該第二發光層包括第二主發光材料及過渡金屬有機錯合物；形成於第二發光層上之電子傳輸層，使該第二發光層夾置於該第一發光層和電子傳輸層之間；以及陰極，係形成於電子傳輸層上，使該電子傳輸層夾置於該第二發光層和陰極之間，其中，該第一主發光材料和第二主發光材料之三重態能階皆大於2.7 eV。In order to achieve the above and other objects, the present invention provides an organic electroluminescent device, comprising: an anode; a hole transport layer formed on the anode; and a first light-emitting layer formed on the hole transport layer to make the electricity a hole transport layer interposed between the anode and the first light emitting layer, the first light emitting layer including the first main light a material and a transition metal organic complex; a second light-emitting layer formed on the first light-emitting layer, the first light-emitting layer being sandwiched between the hole transport layer and the second light-emitting layer, the second light-emitting layer The layer includes a second main luminescent material and a transition metal organic complex; an electron transport layer formed on the second luminescent layer, the second luminescent layer being sandwiched between the first luminescent layer and the electron transporting layer; and a cathode Formed on the electron transport layer, the electron transport layer being sandwiched between the second light-emitting layer and the cathode, wherein the triplet energy level of the first main light-emitting material and the second main light-emitting material are both greater than 2.7 eV .
本發明另提供一種有機電激發光元件，包括：陽極；電洞傳輸層，係形成於陽極上；形成於該電洞傳輸層上之第一發光層，使該電洞傳輸層夾置於該陽極和第一發光層之間，該第一發光層包括第一主發光材料、過渡金屬有機錯合物及載子傳輸材料；形成於該第一發光層上之第二發光層，使該第一發光層夾置於該電洞傳輸層和該第二發光層之間，該第二發光層包括第二主發光材料、過渡金屬有機錯合物及載子傳輸材料；電子傳輸層，係形成於第二發光層上，使該第二發光層夾置於該第一發光層和電子傳輸層之間；以及陰極，係形成於電子傳輸層上，使該電子傳輸層夾置於該第二發光層和陰極之間，其中，該第一主發光材料、第二主發光材料及載子傳輸材料之三重態能階皆大於2.7 eV。The present invention further provides an organic electroluminescent device, comprising: an anode; a hole transport layer formed on the anode; and a first light-emitting layer formed on the hole transport layer, the hole transport layer being sandwiched between the hole Between the anode and the first luminescent layer, the first luminescent layer comprises a first main luminescent material, a transition metal organic complex and a carrier transporting material; and a second luminescent layer formed on the first luminescent layer, such that a light emitting layer is interposed between the hole transport layer and the second light emitting layer, the second light emitting layer comprises a second main light emitting material, a transition metal organic complex and a carrier transport material; and an electron transport layer is formed On the second luminescent layer, the second luminescent layer is sandwiched between the first luminescent layer and the electron transporting layer; and the cathode is formed on the electron transporting layer, so that the electron transporting layer is sandwiched between the second luminescent layer The triplet energy level of the first main luminescent material, the second main luminescent material and the carrier transporting material is greater than 2.7 eV.
在本發明之具有載子傳輸材料的有機電激發光元件中，係利用載子傳輸材料，摻雜於有機發光層中，以輔助載子注入。此外，視需要地，本發明之第一及第二主發光 材料之三重態能階與該載子傳輸材料之三重態能階大於過渡金屬有機錯合物之三重態能階，以進一步避免能量回傳和降低有機電激發光元件之操作電壓，且同時能提高該元件的發光效率。In the organic electroluminescent device having a carrier transport material of the present invention, it is doped into the organic light-emitting layer by a carrier transport material to assist carrier injection. In addition, the first and second main illuminations of the present invention are optionally required The triplet energy level of the material and the triplet energy level of the carrier transport material are greater than the triplet energy level of the transition metal organic complex to further avoid energy return and reduce the operating voltage of the organic electroluminescent element, and at the same time Improve the luminous efficiency of the component.
以下將藉由特定具體實例進一步說明本發明之特點，但非用以限制本發明之範疇。The features of the present invention are further illustrated by the following specific examples, but are not intended to limit the scope of the invention.
第1A圖為本發明之有機電激發光元件之剖面結構示意圖。於本發明之具體實例中，有機電激發光元件100由下而上依序包含基板102、陽極104、電洞傳輸層106、有機發光層108、電子傳輸層109、以及陰極112。於一具體實例中，本發明之基材102與陽極104皆為透明材質。又，基材102之實例包括，但不限於玻璃基材或塑膠基材，且以塑膠基材所製成的有機電激發光元件會具有可撓性的優點，而陽極104之實例包括，但不限於透明導電金屬氧化物薄膜，例如，銦錫氧化物(indium tin oxide，簡稱ITO)。Fig. 1A is a schematic cross-sectional view showing the organic electroluminescent device of the present invention. In a specific example of the present invention, the organic electroluminescent device 100 includes a substrate 102, an anode 104, a hole transport layer 106, an organic light-emitting layer 108, an electron transport layer 109, and a cathode 112 from bottom to top. In one embodiment, the substrate 102 and the anode 104 of the present invention are both transparent materials. Also, examples of the substrate 102 include, but are not limited to, a glass substrate or a plastic substrate, and an organic electroluminescent device made of a plastic substrate may have the advantage of flexibility, and examples of the anode 104 include, but It is not limited to a transparent conductive metal oxide film, for example, indium tin oxide (ITO).
另一方面，如第1B圖所示，於又一具體實施例中，有機電激發光元件可視需要包括複數個電洞傳輸層和電子傳輸層，具體而言，有機電激發光元件200由下而上可依序包含基板202、陽極204、第一電洞傳輸層206、第二電洞傳輸層206’、有機發光層108、第一電子傳輸層209、第二電子傳輸層209’、以及陰極212。此外，第二電子傳輸層亦可以為電子注入層。On the other hand, as shown in FIG. 1B, in another embodiment, the organic electroluminescent device may optionally include a plurality of hole transport layers and electron transport layers, specifically, the organic electroluminescent device 200 is The substrate 202, the anode 204, the first hole transport layer 206, the second hole transport layer 206', the organic light-emitting layer 108, the first electron transport layer 209, the second electron transport layer 209', and Cathode 212. In addition, the second electron transport layer may also be an electron injection layer.
本發明之電洞傳輸層之材料包括，例如，N,N’－雙－(1－萘基)－N,N’－二苯基,1,1’－聯苯－4,4’－二胺(N,N’－bis－(1－naphthyl)－N,N’－diphenyl,1,1’－biphenyl－4,4’－dia mine，簡稱NPB)、雙[4－(p,p’ －二甲基二苯胺基)－苯基]二苯基矽烷(DTASi)或其他滿足本發明需求之材料。於一具體實施例中，第一電洞傳輸層之材料為N,N’－雙－(1－萘基)－N,N’－二苯基，1,1’－聯苯－4,4’－二胺，而第二電洞傳輸層的材料為雙[4－(p,p’ －二甲基二苯胺基)－苯基]二苯基矽烷。The material of the hole transport layer of the present invention includes, for example, N,N'-bis-(1-naphthyl)-N,N'-diphenyl, 1,1'-biphenyl-4,4'-di Amine (N, N'-bis-(1-naphthyl)-N, N'-diphenyl, 1,1'-biphenyl-4, 4'-dia mine, NPB), bis [4-( p, p' -Dimethyldiphenylamino)-phenyl]diphenyldecane (DTASi) or other materials which satisfy the needs of the present invention. In one embodiment, the material of the first hole transport layer is N,N'-bis-(1-naphthyl)-N,N'-diphenyl, 1,1'-biphenyl-4,4 '-Diamine, and the material of the second hole transport layer is bis[4-( p,p' -dimethyldiphenylamino)-phenyl]diphenylnonane.
第2圖係本發明之有機發光層208之示意圖，該有機發光層包括第一發光層218、形成於第一發光層上之第二發光層228，且該第一發光層係與電洞傳輸層接觸，而第二發光層則與電子傳輸層接觸。2 is a schematic view of an organic light-emitting layer 208 of the present invention. The organic light-emitting layer includes a first light-emitting layer 218, a second light-emitting layer 228 formed on the first light-emitting layer, and the first light-emitting layer and the hole are transmitted. The layers are in contact and the second luminescent layer is in contact with the electron transport layer.
於一態樣中，第一發光層包括第一主發光材料及過渡金屬有機錯合物，第二發光層包括第二主發光材料及過渡金屬有機錯合物，其中，第一主發光材料和第二主發光材料之三重態能階皆大於2.7 eV。另一方面，亦可令第一主發光材料及第二主發光材料之三重態能階皆大於該過渡金屬有機錯合物之三重態能階。In one aspect, the first luminescent layer includes a first main luminescent material and a transition metal organic complex, and the second luminescent layer includes a second main luminescent material and a transition metal organic complex, wherein the first main luminescent material and The triplet energy level of the second main luminescent material is greater than 2.7 eV. On the other hand, the triplet energy level of the first main luminescent material and the second main luminescent material may be greater than the triplet energy level of the transition metal organic complex.
於另一態樣中，第一發光層包括第一主發光材料、過渡金屬有機錯合物及載子傳輸材料，第二發光層包括第二主發光材料、過渡金屬有機錯合物及載子傳輸材料，其中，第一主發光材料、第二主發光材料及載子傳輸材料之三重態能階皆大於2.7 eV。另一方面，亦可令第一主發 光材料及第二主發光材料之三重態能階皆大於該過渡金屬有機錯合物之三重態能階。In another aspect, the first luminescent layer comprises a first main luminescent material, a transition metal organic complex and a carrier transport material, and the second luminescent layer comprises a second main luminescent material, a transition metal organic complex and a carrier The transmission material, wherein the first main luminescent material, the second main luminescent material, and the carrier transport material have a triplet energy level greater than 2.7 eV. On the other hand, it can also make the first main hair The triplet energy level of the optical material and the second main luminescent material is greater than the triplet energy level of the transition metal organic complex.
於本發明之一具體實施中，該第一主發光材料和第二主發光材料係為不同之材料。In one embodiment of the invention, the first primary luminescent material and the second primary luminescent material are different materials.
於較佳實施例中，第一發光層係位於陽極和第二發光層之間。In a preferred embodiment, the first luminescent layer is between the anode and the second luminescent layer.
於本發明之有機電激發光元件中，該第一主發光材料和該電洞傳輸層之最高電子佔據能階(HOMO)之差小於1 eV。In the organic electroluminescent device of the present invention, the difference between the highest electron occupation level (HOMO) of the first main luminescent material and the hole transport layer is less than 1 eV.
又，於本發明之又一具體實施例中，該第二主發光材料和該電子傳輸層之最低電子未佔據能階(LUMO)之差小於1 eV。或者，於另一具體實施例中，可使該第一主發光材料和該電洞傳輸層之最高電子佔據能階(HOMO)之差小於1 eV且該第二主發光材料和該電子傳輸層之最低電子未佔據能階(LUMO)之差亦小於1 eV。Moreover, in still another embodiment of the present invention, a difference between a lowest electron unoccupied energy level (LUMO) of the second main luminescent material and the electron transporting layer is less than 1 eV. Alternatively, in another embodiment, the difference between the highest electron occupation level (HOMO) of the first main luminescent material and the hole transport layer may be less than 1 eV and the second main luminescent material and the electron transport layer The difference between the lowest electron unoccupied energy levels (LUMO) is also less than 1 eV.
於本發明之一具體實施例中，第一主發光材料和第二主發光材料係為不同之材料。In a specific embodiment of the invention, the first primary luminescent material and the second primary luminescent material are different materials.
於另一具體實施例中，該第一主發光材料係選自咔唑類(carbazole－based)類化合物或含三級胺芳香族類化合物。較佳地，在發光層中可選用一種或多種的主發光材料，具體而言，第一主發光材料係選自9－(4－第三－丁基苯)－3,6－雙(三苯基矽基)－9H－咔唑(CzSi)、2,2’－雙(4－咔唑基苯基)－1,1’－聯苯(4CzPBP)、4,4’－雙(9－咔唑基)－2,2’－二甲基－聯苯(CDBP)、N,N’ －二咔唑基－2,5－苯 (m CP)、3,5－雙(9－咔唑基)四苯基矽烷(SimCP)、三[4－(9－苯基芴－9－基)苯基]胺(TFTPA)、4,4’,4’－三(N －咔唑基)三苯基胺(TCTA)、雙[4－(p,p’ －二甲基二苯胺基)－苯基]二苯基矽烷(DTASi)、1,1－雙[4－[N,N－二(p－甲苯基)胺基]苯基]環己烷(TAPC)或其組成之群組。In another embodiment, the first primary luminescent material is selected from the group consisting of a carbazole-based compound or a tertiary amine-containing aromatic compound. Preferably, one or more main luminescent materials are optionally used in the luminescent layer, in particular, the first main luminescent material is selected from the group consisting of 9-(4-t-butylbenzene)-3,6-bis (three Phenylfluorenyl)-9H-carbazole (CzSi), 2,2'-bis(4-carbazolylphenyl)-1,1'-biphenyl (4CzPBP), 4,4'-bis (9- Oxazolyl)-2,2'-dimethyl-biphenyl (CDBP), N,N' -dicarbazolyl-2,5-benzene ( m CP), 3,5-bis(9-carbazole Tetraphenyl decane (SimCP), tris[4-(9-phenylfluoren-9-yl)phenyl]amine (TFTPA), 4,4',4'-tris( N -carbazolyl) Phenylamine (TCTA), bis[4-( p,p' -dimethyldiphenylamino)-phenyl]diphenylnonane (DTASi), 1,1-bis[4-[N,N-di (p-Tolyl)amino]phenyl]cyclohexane (TAPC) or a group of its constituents.
於本發明之一具體實施例中，第二主發光材料可選自膦(phosphine oxide－based)、三嗪類化合物或咪唑類化合物。較佳地，在第二發光層中亦可選用一種或多種的第二主發光材料，具體而言，第二主發光材料係選自膦氧化物2,8－雙(二苯基膦基)二苯并呋喃(DPDBF)、2,8－雙(二苯基膦基)二苯并噻吩(PPT)、2,4,6－咔唑并－1,3,5－三嗪(TRZ)、1,3,5－三(苯基苯并咪唑－2－基)苯(TPBI)或其組成之群組。In one embodiment of the invention, the second primary luminescent material may be selected from the group consisting of phosphine oxide-based, triazine-based compounds, or imidazole compounds. Preferably, one or more second main luminescent materials are also selected in the second luminescent layer. Specifically, the second main luminescent material is selected from the group consisting of phosphine oxide 2,8-bis(diphenylphosphino). Dibenzofuran (DPDBF), 2,8-bis(diphenylphosphino)dibenzothiophene (PPT), 2,4,6-oxazolo-1,3,5-triazine (TRZ), 1,3,5-Tris(phenylbenzimidazol-2-yl)benzene (TPBI) or a group thereof.
於本發明之有機電激發光元件中，第一發光層所含之過渡有機金屬錯合物和第二發光層所含之過渡有機金屬錯合物可為相同或不同之過渡有機金屬錯合物。In the organic electroluminescent device of the present invention, the transition organometallic complex contained in the first luminescent layer and the transition organometallic complex contained in the second luminescent layer may be the same or different transition organometallic complexes. .
於一具體實施例中，過渡金屬有機錯合物可選自雙(4,6－二氟苯基)－吡啶－N,C2’ )吡啶甲酸銥(III)(FIrpic)、雙(4’,6’－二氟苯基吡啶)肆(1－吡唑基)硼酸銥(III)(FIr6)、雙(4,6－二氟苯基吡啶)(3－(三氟甲基)－5－(吡啶－2－基)－1,2,4－三嗪酯銥(III)(FIrtaz)或雙(4,6－二氟苯基吡啶)(5－(吡啶－2－基)－1H －－四嗪酯銥(III)(FIrN4)。In one embodiment, the transition metal organic complex may be selected from the group consisting of bis(4,6-difluorophenyl)-pyridine-N,C 2 ' )pyridine ruthenate (III) (FIrpic), double (4',6'-difluorophenylpyridine) ruthenium (1-pyrazolyl)borate (III) (FIr6), bis(4,6-difluorophenylpyridine)(3-(trifluoromethyl)-5 -(pyridin-2-yl)-1,2,4-triazine ester 铱(III)(FIrtaz) or bis(4,6-difluorophenylpyridine)(5-(pyridin-2-yl)-1 H -tetrazinyl ester ruthenium (III) (FIrN4).
於具有載子傳輸層之具體實施例中，載子傳輸材料可
選自具有下式(I)或式(II)之含三級胺芳香族化合物：
或者，於一較佳具體實施例中，載子傳輸材料可選自三[4－(9－苯基芴－9－基)苯基]胺(TFTPA)、4,4’,4’－三(N －咔唑基)三苯基胺(TCTA)、雙[4－(p,p’ －二甲基二苯胺基)－苯基]二苯基矽烷(DTASi)、1,1－雙[4－[N,N－二(p－甲苯基)胺基]苯基]環己烷(TAPC)或其組成之群組。Alternatively, in a preferred embodiment, the carrier transport material may be selected from the group consisting of tris[4-(9-phenylfluoren-9-yl)phenyl]amine (TFTPA), 4,4', 4'-three ( N -carbazolyl)triphenylamine (TCTA), bis[4-( p,p' -dimethyldiphenylamino)-phenyl]diphenyldecane (DTASi), 1,1-double [ 4-[N,N-bis(p-tolyl)amino]phenyl]cyclohexane (TAPC) or a group thereof.
下列化學式及表一例舉本發明之實施例中所採用之主發光材料、載子傳輸材料以及磷光材料。The following chemical formulas and tables exemplify the main luminescent materials, carrier transport materials, and phosphorescent materials used in the examples of the present invention.
由表一可得知，本發明所採用之第一及第二主發光材料之三重態能階與載子傳輸材料之三重態能階需分別大於過渡金屬有機錯合物之三重態能階，其中，該第一和第二主發光材料之三重態能階皆大於2.7 eV，及載子傳輸 材料之三重態能階大於2.7 eV。It can be seen from Table 1 that the triplet energy level of the first and second main luminescent materials used in the present invention and the triplet energy level of the carrier transport material are respectively greater than the triplet energy level of the transition metal organic complex. Wherein the triplet energy levels of the first and second main luminescent materials are greater than 2.7 eV, and the carrier transmission The triplet energy level of the material is greater than 2.7 eV.
於本發明之有機電激發光元件之一具體實施例中，以摻雜有載子傳輸材料之藍色發光層為例，為避免藍色發光層所產生之能量，轉移至載子傳輸材料上，主發光材料之三重態能階與所摻雜之載子傳輸材料之三重態能階皆須大於發藍光之磷光材料的三重態能階。In a specific embodiment of the organic electroluminescent device of the present invention, the blue light-emitting layer doped with the carrier transport material is taken as an example, and the energy generated by the blue light-emitting layer is prevented from being transferred to the carrier transport material. The triplet energy level of the main luminescent material and the triplet energy level of the doped carrier transport material must be greater than the triplet energy level of the blue light emitting phosphor material.
因此，參考第1圖，當於本發明之有機電激發光元件外加一電壓時，電子與電洞會藉由電子傳輸層109與電洞傳輸層106而傳輸至有機發光層108，隨後，電子與電洞會在於有機發光層108中再結合而放出光。此時，由於主發光材料之三重態能階與載子傳輸材料之三重態能階分別大於過渡有機金屬錯合物之三重態能階，且第一發光層與陽極之HOMO能階差的絕對值係小於1 eV，及第二發光層與陰極之LUMO能階差的絕對值係小於1 eV，所以，所需要的元件操作電壓較低，進而能同時提高元件的發光效率。Therefore, referring to FIG. 1, when a voltage is applied to the organic electroluminescent device of the present invention, electrons and holes are transmitted to the organic light-emitting layer 108 by the electron transport layer 109 and the hole transport layer 106, and subsequently, electrons. The holes and the holes may be recombined in the organic light-emitting layer 108 to emit light. At this time, since the triplet energy level of the main luminescent material and the triplet energy level of the carrier transport material are respectively greater than the triplet energy level of the transition metal complex, and the absolute difference of the HOMO energy difference between the first luminescent layer and the anode The value is less than 1 eV, and the absolute value of the LUMO energy difference between the second luminescent layer and the cathode is less than 1 eV. Therefore, the required component operating voltage is low, and the luminous efficiency of the component can be simultaneously improved.
以下為本發明有機電激發光元件之各實施例之說明，但各層所使用之材料、厚度以及濃度，並非用以限制本發明之範圍。The following is a description of various embodiments of the organic electroluminescent device of the present invention, but the materials, thicknesses, and concentrations used in the various layers are not intended to limit the scope of the present invention.
實施例1Example 1
第一主發光材料係選用4CzPBP，第二主發光材料係選用PPT，第一發光層及第二發光層所含的過渡有機金屬錯合物皆選用FIrpic。依下列流程製備有機電激發光元件。The first main luminescent material is selected from 4CzPBP, the second main luminescent material is selected from PPT, and the transition metal organic complex contained in the first luminescent layer and the second luminescent layer is selected from FIrpic. An organic electroluminescent device was prepared according to the following procedure.
於厚度0.7 mm之玻璃基板上形成150 nm之銦錫氧化 物(indium tin oxide，ITO)作為陽極後，於該陽極上以熱蒸鍍方式，鍍上厚度45 nm之NPB作為第一電洞傳輸層，接著以熱蒸鍍方式於第一電洞傳輸層上鍍上厚度15 nm之DTASi作為第二電洞傳輸層。再將第一主發光材料4CzPBP和過渡有機金屬錯合物FIrpic，共蒸鍍形成厚度－10 nm之第一發光層於第二電洞傳輸層上，其中，第一主發光材料和過渡有機金屬錯合物之重量比為85：15(如表二所示)。接著，將重量比分別為85：15之第二主發光材料PPT及過渡有機金屬錯合物FIrpic，共蒸鍍形成厚度10 nm之第二發光層於第一發光層上。之後，於第二發光層上，以熱蒸鍍方式鍍上厚度為25 nm之4,7－二苯基－1,10－啡咯啉(4,7－diphenyl－1,10－phenanthroline，以下簡稱Bphen)作為電子傳輸層。接著，將重量比分別為20：80之碳酸銫(Cs2 CO3 )和Bphen共同蒸鍍於電子傳輸層上，形成厚度為20 nm之電子注入層。最後以熱蒸鍍方式，形成厚度為120 nm之鋁陰極。After 150 nm of indium tin oxide (ITO) was formed on the glass substrate with a thickness of 0.7 mm as an anode, NPB with a thickness of 45 nm was plated on the anode as the first hole. The layer is then plated with a thickness of 15 nm of DTASi as a second hole transport layer on the first hole transport layer by thermal evaporation. The first main luminescent material 4CzPBP and the transition metal complex complex FIrpic are co-evaporated to form a first luminescent layer having a thickness of -10 nm on the second hole transport layer, wherein the first main luminescent material and the transitional organic metal The weight ratio of the complex was 85:15 (as shown in Table 2). Next, a second main light-emitting material PPT and a transition metal complex complex FIrpic having a weight ratio of 85:15, respectively, were co-deposited to form a second light-emitting layer having a thickness of 10 nm on the first light-emitting layer. Thereafter, on the second luminescent layer, 4,7-diphenyl-1,10-morpholine (4,7-diphenyl-1,10-phenanthroline, below thickness) of 25 nm was plated by thermal evaporation. Referred to as Bphen) as an electron transport layer. Next, cesium carbonate (Cs 2 CO 3 ) and Bphen, each having a weight ratio of 20:80, were co-evaporated on the electron transport layer to form an electron injecting layer having a thickness of 20 nm. Finally, an aluminum cathode having a thickness of 120 nm was formed by thermal evaporation.
在本實施例中，第一主發光材料與相鄰的第二電洞傳輸材料之最高電子佔據能階(HOMO)差為0.4 eV，第二主發光材料與相鄰的電子傳輸材料之最低電子佔據能階(LUMO)差為0.1 eV，而第一發光層及第二發光層之成分比例，以及在元件亮度為1000 cd/m2 之電流效率及操作電壓之測試結果如表二所示。In this embodiment, the highest electron occupation level (HOMO) difference between the first main luminescent material and the adjacent second hole transport material is 0.4 eV, and the lowest electron of the second main luminescent material and the adjacent electron transport material The difference in occupied potential (LUMO) is 0.1 eV, and the composition ratios of the first light-emitting layer and the second light-emitting layer, and the current efficiency and operating voltage at a device luminance of 1000 cd/m 2 are shown in Table 2.
實施例2Example 2
除了第一主發光材料係選用CzSi，第二主發光材料 係選用PPT，第一發光層及第二發光層所含的過渡有機金屬錯合物皆選用Firpic外，根據實施例1所述流程製備實施例2之有機電激發光元件。In addition to the first main luminescent material, CzSi is selected, and the second main luminescent material is used. The PPT was selected, and the organic electroluminescent device of Example 2 was prepared according to the procedure described in Example 1 except that the transition metal-organic complex contained in the first light-emitting layer and the second light-emitting layer was selected from Firpic.
在本實施例中，第一主發光材料與電洞傳輸材料之最高電子佔據能階(HOMO)差為0.3 eV，第二主發光材料與相鄰的電子傳輸材料之最低電子佔據能階(LUMO)差為0.1 eV，而第一發光層及第二發光層之成分比例，以及在元件亮度為1000 cd/m2 之電流效率及操作電壓之測試結果如表二所示。In this embodiment, the highest electron occupation level (HOMO) difference between the first main luminescent material and the hole transport material is 0.3 eV, and the lowest electron occupying energy level of the second main luminescent material and the adjacent electron transporting material (LUMO) The difference is 0.1 eV, and the composition ratios of the first light-emitting layer and the second light-emitting layer, and the current efficiency and operating voltage at a device luminance of 1000 cd/m 2 are shown in Table 2.
比較例1Comparative example 1
比較例1之有機電激發光元件僅包括單層發光層，主發光材料係選用4CzPBP，過渡有機金屬錯合物係選用FIrpic，並依下列流程製備有機電激發光元件。The organic electroluminescent device of Comparative Example 1 includes only a single layer of the light-emitting layer, the main light-emitting material is selected from 4CzPBP, and the transition metal-metal complex is selected from FIrpic, and the organic electroluminescent device is prepared according to the following procedure.
於厚度0.7 mm之玻璃基板上形成150 nm之銦錫氧化物(indium tin oxide，ITO)作為陽極後，於該陽極上以熱蒸鍍方式，鍍上厚度45 nm之NPB作為第一電洞傳輸層，接著以熱蒸鍍方式於第一電洞傳輸層上，鍍上厚度15 nm之DTASi作為第二電洞傳輸層。再將主發光材料4CzPBP和過渡有機金屬錯合物FIrpic，共蒸鍍一厚度20 nm之發光層於第二電洞傳輸層上。接著，於發光層上，以熱蒸鍍方式鍍上厚度為25 nm之Bphen作為電子傳輸層。接著，將重量比分別為20：80之碳酸銫(Cs2 CO3 )和Bphen共同蒸鍍於電子傳輸層上，形成厚度為20 nm之電子注入層。最後以熱蒸鍍方式，形成厚度為120 nm之鋁 陰極。After 150 nm of indium tin oxide (ITO) was formed on the glass substrate with a thickness of 0.7 mm as an anode, NPB with a thickness of 45 nm was plated on the anode as the first hole. The layer is then thermally deposited on the first hole transport layer, and DTASi having a thickness of 15 nm is plated as the second hole transport layer. Then, the main luminescent material 4CzPBP and the transition metal complex complex FIrpic are co-deposited with a luminescent layer having a thickness of 20 nm on the second hole transport layer. Next, Bphen having a thickness of 25 nm was plated on the light-emitting layer by thermal evaporation as an electron transport layer. Next, cesium carbonate (Cs 2 CO 3 ) and Bphen, each having a weight ratio of 20:80, were co-evaporated on the electron transport layer to form an electron injecting layer having a thickness of 20 nm. Finally, an aluminum cathode having a thickness of 120 nm was formed by thermal evaporation.
發光層之成分比例，以及在元件亮度為1000 cd/m2 之電流效率及操作電壓之測試結果如表二所示。The composition ratio of the light-emitting layer, and the current efficiency and operating voltage at a device luminance of 1000 cd/m 2 are shown in Table 2.
比較例2Comparative example 2
比較例2之有機電激發光元件僅包括單層發光層，主發光材料係選用CzSi，過渡有機金屬錯合物係選用FIrpic，並根據比較例1所述流程製備有機電激發光元件。The organic electroluminescent device of Comparative Example 2 includes only a single layer of the light-emitting layer, the main light-emitting material is CzSi, the transition metal-metal complex is FIrpic, and the organic electroluminescent device is prepared according to the procedure described in Comparative Example 1.
發光層之成分比例，以及在元件亮度為1000 cd/m2 之電流效率及操作電壓之測試結果如表二所示。The composition ratio of the light-emitting layer, and the current efficiency and operating voltage at a device luminance of 1000 cd/m 2 are shown in Table 2.
比較例3Comparative example 3
比較例3之有機電激發光元件僅包括單層發光層，主發光材料係選用PPT，過渡有機金屬錯合物係選用FIrpic，並根據比較例1所述流程製備有機電激發光元件。The organic electroluminescent device of Comparative Example 3 includes only a single layer of the light-emitting layer, the main light-emitting material is PPT, the transition metal-metal complex is FIrpic, and the organic electroluminescent device is prepared according to the procedure described in Comparative Example 1.
發光層之成分比例，以及在元件亮度為1000 cd/m2 之電流效率及操作電壓之測試結果如表二所示。The composition ratio of the light-emitting layer, and the current efficiency and operating voltage at a device luminance of 1000 cd/m 2 are shown in Table 2.
比較例4Comparative example 4
比較例4之有機電激發光元件包括第一及第二發光層，其中，第一主發光材料係選用PPT，第二主發光材料係選用4CzPBP，過渡有機金屬錯合物皆選用FIrpic，並根據實施例1所述流程製備有機電激發光元件。The organic electroluminescent device of Comparative Example 4 includes first and second luminescent layers, wherein the first main luminescent material is PPT, the second main luminescent material is 4CzPBP, and the transitional organometallic complex is FIRP, and The organic electroluminescent device was prepared in the procedure described in Example 1.
第一發光層及第二發光層之成分比例，以及在元件亮度為1000 cd/m2 之電流效率及操作電壓之測試結果如表二所示。The composition ratios of the first light-emitting layer and the second light-emitting layer, and the current efficiency and operating voltage at a device luminance of 1000 cd/m 2 are shown in Table 2.
如表二所示，當本發明之元件裝置之發光層由包括兩個不同的主發光材料組成(實施例1和2)時，相較於僅具有單一主發光材料之元件(比較例1~3)，本發明之元件效率能有效提升1.8~2.0倍。As shown in Table 2, when the light-emitting layer of the component device of the present invention consists of two different main luminescent materials (Examples 1 and 2), compared to an element having only a single main luminescent material (Comparative Example 1~) 3), the component efficiency of the present invention can be effectively increased by 1.8 to 2.0 times.
另一方面由比較例4的結果顯示，當第一發光層中的主發光材料與電洞傳輸層的HOMO能階差大於1 eV，操作電壓較高且元件效率亦較實施例1和2差。On the other hand, the results of Comparative Example 4 show that when the HOMO energy difference between the main luminescent material and the hole transport layer in the first luminescent layer is greater than 1 eV, the operating voltage is higher and the component efficiency is also inferior to that of Embodiments 1 and 2. .
實施例3Example 3
除了在發光層中復包括載子傳輸材料TCTA並藉由共蒸鍍之方式形成發光層外，根據實施例1所述流程製備有機電激發光元件。An organic electroluminescent device was prepared according to the procedure described in Example 1, except that the carrier transport material TCTA was further included in the light-emitting layer and the light-emitting layer was formed by co-evaporation.
在本實施例中，第一主發光材料與電洞傳輸材料之最高電子佔據能階差為0.4 eV，第二主發光材料與相鄰的電子傳輸材料之最低電子佔據能階(LUMO)差為0.1 eV，而第一發光層及第二發光層之成分比例，以及在元件亮度為1000 cd/m2 之電流效率及操作電壓之測試結果如表三所示。In this embodiment, the highest electron occupying energy difference of the first main luminescent material and the hole transporting material is 0.4 eV, and the lowest electron occupying energy level (LUMO) difference between the second main luminescent material and the adjacent electron transporting material is 0.1 eV, and the composition ratio of the first light-emitting layer and the second light-emitting layer, and the current efficiency and operating voltage at a device luminance of 1000 cd/m 2 are shown in Table 3.
實施例4Example 4
第一主發光材料係選用4CzPBP，第二主發光材料係選用PPT，第一發光層及第二發光層皆摻雜15 wt%之FIrpic，及載子傳輸材料則摻雜10 wt%之TCTA，並根據實施例3所述流程製備有機電激發光元件。The first main luminescent material is 4CzPBP, the second main luminescent material is PPT, the first luminescent layer and the second luminescent layer are doped with 15 wt% of FIrpic, and the carrier transporting material is doped with 10 wt% of TCTA. An organic electroluminescent device was prepared according to the procedure described in Example 3.
第一發光層及第二發光層之成分比例，以及在元件亮度為1000 cd/m2 之電流效率及操作電壓之測試結果如表三所示。The composition ratios of the first light-emitting layer and the second light-emitting layer, and the current efficiency and operating voltage at a device luminance of 1000 cd/m 2 are shown in Table 3.
實施例5Example 5
第一主發光材料係選用4CzPBP，第二主發光材料係選用PPT，第一發光層及第二發光層皆摻雜20 wt%之FIrpic，及載子傳輸材料則摻雜10 wt%之TCTA，並根據實施例3所述流程製備有機電激發光元件。The first main luminescent material is 4CzPBP, the second main luminescent material is PPT, the first luminescent layer and the second luminescent layer are doped with 20 wt% of FIrpic, and the carrier transporting material is doped with 10 wt% of TCTA. An organic electroluminescent device was prepared according to the procedure described in Example 3.
第一發光層及第二發光層之成分比例，以及在元件亮度為1000 cd/m2 之電流效率及操作電壓之測試結果如表三所示。The composition ratios of the first light-emitting layer and the second light-emitting layer, and the current efficiency and operating voltage at a device luminance of 1000 cd/m 2 are shown in Table 3.
實施例6Example 6
第一主發光材料係選用4CzPBP，第二主發光材料係選用PPT，第一發光層及第二發光層皆摻雜15 wt%之FIrpic，及載子傳輸材料則摻雜15 wt%之TCTA，並根據實施例3所述流程製備有機電激發光元件。The first main luminescent material is 4CzPBP, the second main luminescent material is PPT, the first luminescent layer and the second luminescent layer are doped with 15 wt% of FIrpic, and the carrier transporting material is doped with 15 wt% of TCTA. An organic electroluminescent device was prepared according to the procedure described in Example 3.
第一發光層及第二發光層之成分比例，以及在元件亮度為1000 cd/m2 之電流效率及操作電壓之測試結果如表三所示。The composition ratios of the first light-emitting layer and the second light-emitting layer, and the current efficiency and operating voltage at a device luminance of 1000 cd/m 2 are shown in Table 3.
比較例5Comparative Example 5
比較例5之有機電激發光元件包括第一及第二發光層，其中，第一主發光材料係選用PPT，第二主發光材料係選用4CzPBP，第一發光層及第二發光層皆摻雜15 wt%之FIrpic，及載子傳輸材料則摻雜10 wt%之TCTA，並根據實施例3所述流程製備有機電激發光元件。The organic electroluminescent device of Comparative Example 5 includes first and second luminescent layers, wherein the first main luminescent material is PPT, and the second main luminescent material is 4CzPBP, and the first luminescent layer and the second luminescent layer are doped. 15 wt% of FIrpic, and the carrier transport material were doped with 10 wt% of TCTA, and an organic electroluminescent device was prepared according to the procedure described in Example 3.
第一發光層及第二發光層之成分比例，以及在元件亮度為1000 cd/m2 之電流效率及操作電壓之測試結果如表三所示。The composition ratios of the first light-emitting layer and the second light-emitting layer, and the current efficiency and operating voltage at a device luminance of 1000 cd/m 2 are shown in Table 3.
根據表三所示之結果，當在本發明之第一及第二發光層中，分別再添加載子傳輸材料(實施例3~6)時，元件效率可以較實施例1之元件再提升1.3倍。而相較於單一發光層之元件(比較例1~3)，實施例3~6元件更提升效率達2.4~3.3倍。According to the results shown in Table 3, when the carrier transport material (Examples 3 to 6) is additionally added to the first and second light-emitting layers of the present invention, the component efficiency can be further increased by 1.3 compared with the component of the embodiment 1. Times. Compared with the components of the single light-emitting layer (Comparative Examples 1 to 3), the components of Examples 3 to 6 have an improvement efficiency of 2.4 to 3.3 times.
另外，在比較例5中，第一發光層中的第一主發光材料與電洞傳輸層的HOMO能階差大於1 eV，即使在第一及第二發光層中亦包含載子傳輸材料，比較例5之元件效率亦較本發明之元件為差。In addition, in Comparative Example 5, the HOMO energy difference of the first main luminescent material and the hole transport layer in the first luminescent layer is greater than 1 eV, and even if the carrier transport material is included in the first and second luminescent layers, The component efficiency of Comparative Example 5 was also inferior to that of the device of the present invention.
由以上實施例及比較例可知，有機發光層中第一及第二主發光材料之三重態能階、與載子傳輸材料之三重態能階，分別需大於磷光材料之三重態能階，且較佳地，需大於2.7 eV；且更佳地，第一主發光材料與電洞傳輸層的HOMO能階差需小於1 eV。如此，能同時降低有機電激發光元件之操作電壓以及顯著提高元件的發光效率。It can be seen from the above embodiments and comparative examples that the triplet energy level of the first and second main luminescent materials in the organic luminescent layer and the triplet energy level of the carrier transport material are respectively greater than the triplet energy level of the phosphorescent material, and Preferably, it is greater than 2.7 eV; and more preferably, the HOMO energy step difference between the first primary luminescent material and the hole transport layer needs to be less than 1 eV. In this way, the operating voltage of the organic electroluminescent device can be simultaneously reduced and the luminous efficiency of the device can be significantly improved.
雖然本發明之實施例揭露如上所述，然並非用以限定本發明，任何熟習相關技藝者，在不脫離本發明之精神和範圍內，舉凡依本發明申請範圍所述之形狀、構造、特徵及精神當可做些許之變更，因此本發明之專利保護範圍須視本說明書所附之申請專利範圍所界定者為準。Although the embodiments of the present invention are disclosed above, it is not intended to limit the present invention, and those skilled in the art, regardless of the spirit and scope of the present invention, the shapes, structures, and features described in the scope of the present application. And the spirit of the invention is subject to change. Therefore, the scope of patent protection of the present invention is subject to the scope of the patent application attached to the specification.
100、200‧‧‧有機電激發光元件100,200‧‧‧Organic electroluminescent components
102、202‧‧‧基板102, 202‧‧‧ substrate
104、204‧‧‧陽極104, 204‧‧‧ anode
106‧‧‧電洞傳輸層106‧‧‧ hole transport layer
108、208‧‧‧有機發光層108, 208‧‧‧ organic light-emitting layer
109‧‧‧電子傳輸層109‧‧‧Electronic transport layer
112、212‧‧‧陰極112, 212‧‧‧ cathode
206‧‧‧第一電洞傳輸層206‧‧‧First hole transport layer
206’‧‧‧第二電洞傳輸層206’‧‧‧Second hole transport layer
209‧‧‧第一電子傳輸層209‧‧‧First electron transport layer
209’‧‧‧第二電子傳輸層209’‧‧‧Second electron transport layer
218‧‧‧第一發光層218‧‧‧First luminescent layer
228‧‧‧第二發光層228‧‧‧second luminescent layer
第1A圖為本發明一實施例之有機電激發光元件之剖面結構示意圖；第1B圖為本發明又一實施例之有機電激發光元件之 剖面結構示意圖；以及第2圖為本發明之用於有機電激發光元件之有機發光層結構示意圖。1A is a cross-sectional structural view of an organic electroluminescent device according to an embodiment of the present invention; FIG. 1B is a view showing an organic electroluminescent device according to still another embodiment of the present invention; Schematic diagram of the cross-sectional structure; and Figure 2 is a schematic view showing the structure of the organic light-emitting layer for the organic electroluminescent device of the present invention.
100‧‧‧有機電激發光元件100‧‧‧Organic electroluminescent components
102‧‧‧基板102‧‧‧Substrate
104‧‧‧陽極104‧‧‧Anode
106‧‧‧電洞傳輸層106‧‧‧ hole transport layer
108‧‧‧有機發光層108‧‧‧Organic light-emitting layer
109‧‧‧電子傳輸層109‧‧‧Electronic transport layer
112‧‧‧陰極112‧‧‧ cathode
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| TWI229569B (en) * | 2003-10-30 | 2005-03-11 | Guan-Jang Peng | Light emitting device and method for producing the same |
| TW200628448A (en) * | 2004-12-08 | 2006-08-16 | Koninkl Philips Electronics Nv | Carbazole compounds |
| US20070222376A1 (en) * | 2006-03-21 | 2007-09-27 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting element, light-emitting device, and electronic device |
| TWI297353B (en) * | 2005-11-10 | 2008-06-01 | Au Optronics Corp | Phosphorescent organic light-emitting diodes |
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| TW200628448A (en) * | 2004-12-08 | 2006-08-16 | Koninkl Philips Electronics Nv | Carbazole compounds |
| TWI297353B (en) * | 2005-11-10 | 2008-06-01 | Au Optronics Corp | Phosphorescent organic light-emitting diodes |
| US20070222376A1 (en) * | 2006-03-21 | 2007-09-27 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting element, light-emitting device, and electronic device |
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